CN104072730B - Siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material and its preparation method and application - Google Patents
Siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material and its preparation method and application Download PDFInfo
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- ZYFNYOIMAVVCHQ-UHFFFAOYSA-N Brc(c1n[s]nc11)cc(I)c1-c(c1n[s]nc1c(Br)c1)c1I Chemical compound Brc(c1n[s]nc11)cc(I)c1-c(c1n[s]nc1c(Br)c1)c1I ZYFNYOIMAVVCHQ-UHFFFAOYSA-N 0.000 description 1
- 0 Cc1c(cc(c2n[s]nc22)Br)c2c(C(C(C(*)=C2)=NSN)=C)c2c1* Chemical compound Cc1c(cc(c2n[s]nc22)Br)c2c(C(C(C(*)=C2)=NSN)=C)c2c1* 0.000 description 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/549—Organic PV cells
Abstract
The present invention relates to a kind of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material, structural formula is:Wherein, R1、R2、R3And R4For C1～C20Alkyl；N is the integer between 1～100.The copolymer material being made up of compound siloledithiophene-bepreparationothiadiazmethod and benzo two (selenole) can form the strongest a kind of donor-receiver structure, on the one hand be conducive to improve the stability of material, on the other hand the band gap of material is advantageously reduced, thus expand sunlight absorption region, improve electricity conversion.Moreover, it relates to the preparation method of a kind of above-mentioned copolymer material and the application in the field such as polymer solar cell device, organic electroluminescence device.
Description
Technical field
The present invention relates to copolymer material field, especially relate to a kind of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material and its preparation method and application.
Background technology
The solaode that preparation cost is low, usefulness is high is always study hotspot and the difficult point of photovoltaic art.The silicon solar cell having been commercialized at present is high due to complex manufacturing, cost so that it is application is restricted.In order to reduce cost, expansive approach scope, people always search for novel solar cell material for a long time.Polymer solar cell device has superior market prospect because the mode large area such as low in raw material price, light weight, flexibility, production technology simple, available coating, printing such as prepare at the advantage.Conjugated copolymer material and C is above reported at SCIENCE (N.SSariciftci, L.Smilowitz, A.J.Heeger, etal.Science, 1992,258,1474) from N.S.Sariciftci in 1992 etc.60Between Photo-induced electron transfer phenomenon after, people have put into numerous studies in terms of polymer solar cell device, and achieve development at full speed.On the one hand but the energy conversion efficiency of traditional polymer solar cell device is the most relatively low, it is due to the carrier mobility of copolymer material several orders of magnitude lower than the mobility of inorganic monocrystalline material；The absorption spectrum of the conjugated copolymer material photovoltaic cell material on the other hand used can not be well matched with solar spectrum.
Summary of the invention
Based on this, it is necessary to provide a kind of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material that can improve photoelectric transformation efficiency and its preparation method and application.
A kind of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material, structural formula is:
Wherein, R1、R2、R3And R4For C1～C20Alkyl；N is the integer between 1～100.
Phenanthrene is by three hexatomic rings and to become, all atoms are in approximately the same plane, there is good electronics cavity transmission ability, and the rigidity of molecule is conducive to improving the thermal stability of material, additionally, the 9 of phenanthrene, 10 easy modifications, the method that can utilize simplicity introduces electron-donating group and electron-accepting group, regulates its confession/electrophilic performance.Diazosulfide unit has the reduction reversibility of excellence, with the work function value of the metallic cathode such as magnesium, aluminum closely, it belongs to short of electricity subtype aromatic cycle compound, there is strong electron-withdrawing power, it is a kind of excellent by body unit, there is preferable electronic transport property, the energy gap of material can also be regulated simultaneously.And the sulphur atom in the radius ratio diazosulfide of selenium atom is big in selenole, more can strengthen the molecule between copolymer material with copolymer material chain overlapping, promote the hopping process of electric charge.Thiophene is five-membered ring structure, has moderate band gap, wider spectral response, preferable heat stability and filming performance.Benzo two (selenole) is the most excellent a kind of acceptor material, and benzo two (selenole) has the advantages such as simple in construction, symmetry, electron delocalization performance be good, and has planar structure, is the most excellent a kind of acceptor material.Thiophene coughs up molecule can form σ *-π * conjugation so that the minimum occupied orbital (LUMO) that thiophene coughs up molecule is relatively low, has good electron affinity and electron mobility simultaneously.Siloledithiophene-bepreparationothiadiazmethod has three five-membered ring structures, has narrow band gap and strong conjugated nature.The copolymer material being made up of compound siloledithiophene-bepreparationothiadiazmethod and benzo two (selenole) can form the strongest a kind of donor-receiver structure, on the one hand be conducive to improve the stability of material, on the other hand the band gap of material is advantageously reduced, thus expand sunlight absorption region, improve electricity conversion.
The preparation method of a kind of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material, comprises the steps:
Thering is provided compound A and compound B, the structural formula of described compound A is:
The structural formula of described compound B is:
R1、R2、R3And R4For C1～C20Alkyl；
In inert protective gas atmosphere; by compound A and compound B according to the ratio that mol ratio is 1:1.5～1.5:1; in catalysts and solvents, carry out Stille coupled reaction, isolated and purified after obtain described siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material that structural formula is following:
N is the integer between 1～100.
Wherein in an embodiment, described catalyst is Pd2(dba)3(three (dibenzalacetone) two palladium), Pd (PPh3)2Cl2(two (triphenylphosphine) palladium chloride) or Pd (PPh3)4(tetrakis triphenylphosphine palladium)；The consumption of described catalyst is the 0.05%～20% of compound A mole.
Wherein in an embodiment, described solvent is oxolane, glycol dimethyl ether, benzene or toluene.
Wherein in an embodiment, the purification procedures of described siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material is: add water in the mixed liquor after Stille coupled reaction and toluene extracts, collect organic facies, organic facies described in decompression distillation and concentration, described organic facies after concentrating again joins in dehydrated alcohol, stirring, solid precipitation is had to separate out, solid precipitation described in collected by suction is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids acetone apparatus,Soxhlet's of gained carries out methanol sedimentation after extracting the most successively, sucking filtration, obtain described siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material of purification.
Wherein in an embodiment, described compound A is made by the steps and obtains:
There is provided and there is the compound C of following structural formula:
R3And R4For C1～C20Alkyl；
In inert protective gas atmosphere; under the conditions of-78 DEG C; it is the ratio of 1:2 by described compound C and n-BuLi according to mol ratio; reaction 1～2 hour in a solvent, then adds tributyltin chloride in reacted mixed liquor, is warming up to room temperature reaction 6 hours after continuing to react 1 hour under the conditions of-78 DEG C; add saturated sodium-chloride water solution and terminate reaction; obtaining described compound A after isolated and purified, wherein, the mole of described tributyltin chloride is 2 times of described compound C mole.
Wherein in an embodiment, the purification procedures of described compound A is: add absolute ether extraction in reacted mixed liquor, collect organic facies, and the moisture removed in described organic facies it is dried with anhydrous sodium sulfate, sucking filtration, collects liquid phase, described liquid phase is carried out rotary evaporation concentration, the crude product obtained is crossed neutral alumina column chromatography, obtains the described compound A of purification.
Wherein in an embodiment, described compound B is made by the steps and obtains:
Thering is provided compound D and compound E, wherein, the structural formula of compound D is:
The structural formula of compound E is:
R1And R2For C1～C20Alkyl；
In inert protective gas atmosphere, in the mixed solution of compound D and compound E, add Bu3N and Pd (OAc)2(acid chloride (II)) carries out ring closure reaction, isolated and purified after obtain described compound B, wherein, the mol ratio of compound D and compound E is 1:2, and the solvent in mixed solution is dimethylformamide, Bu3The mol ratio of N and compound E is 1:1, Pd (OAc)2Mole is compound D mole 10%.
Wherein in an embodiment, the purification procedures of described compound B is:
Use water and dichloromethane to extract reacted mixed liquor, collect organic facies, and be dried the moisture removed in described organic facies with anhydrous sodium sulfate, filter, collect liquid phase, the excess of solvent that decompression is distilled off in described liquid phase, cross silica gel column chromatography, obtain the described compound B of purification.
Above-mentioned preparation method technique is simple, mild condition, react easily controllable, being suitable to industrialized production, siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material prepared can be applied in the fields such as polymer solar cell device, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties and organic laser apparatus.
Accompanying drawing explanation
Fig. 1 is the structural representation of the polymer solar cell device in embodiment 6；
Fig. 2 is the structural representation of the organic electroluminescence device in embodiment 7.
Detailed description of the invention
Mainly in combination with drawings and the specific embodiments, siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material and its preparation method and application is described in further detail below.
Siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material of one embodiment, structural formula is:
Wherein, R1、R2、R3And R4For C1～C20Alkyl；N is the integer between 1～100；Preferably, n is the integer between 19～50.
The copolymer material being made up of compound siloledithiophene-bepreparationothiadiazmethod and benzo two (selenole) can form the strongest a kind of donor-receiver structure, on the one hand be conducive to improve the stability of material, on the other hand the band gap of material is advantageously reduced, thus expand sunlight absorption region, improve electricity conversion.
Additionally, present embodiment additionally provides the preparation method of a kind of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material, comprise the steps:
Thering is provided compound A and compound B, the structural formula of compound A is:
The structural formula of compound B is:
R1、R2、R3And R4For C1～C20Alkyl；
In inert protective gas atmosphere; by compound A and compound B according to the ratio that mol ratio is 1:1.5～1.5:1; in catalysts and solvents, carry out Stille coupled reaction, isolated and purified after obtain structural formula following siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material:
N is the integer between 1～100.
In the present embodiment, the catalyst that above-mentioned preparation process uses is organic palladium catalyst, such as Pd2(dba)3、Pd(PPh3)2Cl2Or Pd (PPh3)4.The consumption of catalyst is the 0.05%～20% of compound A mole.Solvent can be oxolane, glycol dimethyl ether, benzene or toluene, and in course of reaction, solvent needs enough, namely the used in amounts of solvent is completely dissolved reactant and product.The temperature of Stille reaction is 50～120 DEG C, and the response time is 6～100 hours.
Further, the purification procedures of above-mentioned siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material is: add water in the mixed liquor after Stille coupled reaction and toluene extracts, collect organic facies, decompression distillation and concentration organic facies, organic facies after concentrating again joins in dehydrated alcohol, stirring, solid precipitation is had to separate out, collected by suction solid precipitation is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids acetone apparatus,Soxhlet's of gained carries out methanol sedimentation after extracting the most successively, sucking filtration, obtain siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material of purification.
In the present embodiment, compound A is to be made by the steps to obtain:
There is provided and there is the compound C of following structural formula:
R3And R4For C1～C20Alkyl；
In inert protective gas atmosphere; under the conditions of-78 DEG C; it is the ratio of 1:2 by compound C and n-BuLi according to mol ratio; reaction 1～2 hour in a solvent, then adds tributyltin chloride in reacted mixed liquor, is warming up to room temperature reaction 6 hours after continuing to react 1 hour under the conditions of-78 DEG C; add saturated sodium-chloride water solution and terminate reaction; obtaining compound A after isolated and purified, wherein, the mole of tributyltin chloride is 2 times of compound C mole.
Wherein, the purification procedures of compound A is: add absolute ether extraction in reacted mixed liquor, collect organic facies, and the moisture removed in organic facies it is dried with anhydrous sodium sulfate, sucking filtration, collects liquid phase, liquid phase is carried out rotary evaporation concentration, the crude product obtained is crossed neutral alumina column chromatography, obtains the compound A of purification.
Compound B is to be made by the steps to obtain:
Thering is provided compound D and compound E, wherein, the structural formula of compound D is:
The structural formula of compound E is:
R1And R2For C1～C20Alkyl；
In inert protective gas atmosphere, in the mixed solution of compound D and compound E, add Bu3N and Pd (OAc)2Carry out ring closure reaction, isolated and purified after obtain compound B, wherein, the mol ratio of compound D and compound E is 1:2, and the solvent in mixed solution is dimethylformamide, Bu3The mol ratio of N and compound E is 1:1, Pd (OAc)2Mole is compound D mole 10%.
Wherein, the purification procedures of compound B is:
Use water and dichloromethane to extract reacted mixed liquor, collect organic facies, and be dried the moisture removed in organic facies with anhydrous sodium sulfate, filter, collect liquid phase, the excess of solvent that decompression is distilled off in liquid phase, cross silica gel column chromatography, obtain the compound B of purification.
The inert protective gas atmosphere that above-mentioned each preparation of compounds uses can be the atmosphere of inert gases such as nitrogen atmosphere or argon etc..
Above-mentioned preparation method technique is simple, mild condition, react easily controllable, being suitable to industrialized production, siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material prepared can be applied in the fields such as polymer solar cell device, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties and organic laser apparatus.
It it is below specific embodiment part
Embodiment 1 is poly-, and { 4,4-dioctyl-thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) }:
The preparation process of this copolymer material is as follows:
The synthesis of one, 4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles
1, the synthesis of compound 5-nitro-2,1,3 diazosulfide:
22.95g2-amino-5-nitroaniline (0.15mol) and 100ml thionyl chloride (SOCl is added in there-necked flask2), stirring slowly dropping 2ml pyridine, in 80～90 DEG C of back flow reaction 24h after heating；Stopped reaction, is heated to 80 DEG C of rotations and steams the SOCl of excess2After, product is cooled to room temperature, and adds to a large amount of water, stirring, there is precipitate to occur, the solids being collected by filtration is vacuum dried after washing, obtains 21.7g product 5-nitro-2,1,3 diazosulfide, productivity 80%.
2, compound 4,7-bis-bromo-5-nitro-2, the synthesis of 1,3 diazosulfide:
10.35g5-nitro-2,1,3 diazosulfide (60mmol) and the hydrobromic acid of 15ml40wt% is added in there-necked flask, it is warming up to 127 DEG C of backflows, in 30min, slowly drips 11.3ml bromine the 4h that refluxes, heat filtering, refiltering after filtrate cooling, solid washs with substantial amounts of water and is dried, with glacial acetic acid recrystallization once, again with Gossypol recrystallized from chloroform once, obtain 10.2g product 4,7-bis-bromo-5-nitro-2,1,3 diazosulfides, productivity: 50%.
3,4,4 '-two bromo-6, the synthesis of 6 '-dinitro-connection 2,1,3 diazosulfide:
10.2g4 it is sequentially added in there-necked flask, 7-bis-bromo-5-nitro-2, 1, 3 diazosulfides (30mmol), 9.5g copper powder and 90mlN, dinethylformamide (DMF), after being heated to 120 DEG C of reactions 3 hours, stopped reaction, it is cooled to room temperature, add 90ml toluene, stir 30 minutes, filter, successively with saturated aqueous common salt and water washing, merge organic facies, the moisture removed in organic facies it is dried with anhydrous magnesium sulfate, filter, rotary evaporation removes organic solvent, the product dehydrated alcohol recrystallization obtained, obtain 4.7g4, 4 '-two bromo-6, 6 '-dinitro-connection 2, 1, 3 diazosulfides, productivity 30.2%.
The synthesis of 4,4,4 '-two bromo-6,6 '-two iodo-2,1,3-diazosulfides:
In there-necked flask, add 10.3g4,4 '-two bromo-6, oxolane (THF) that 6 '-dinitro-connection 2,1,3 diazosulfide (20mmol), 300ml are dried and 40gSnCl2(200mmol), it is warming up to 100 DEG C, is heated to reflux 10h, stopped reaction, cooling, adjust reacted mixed liquor pH value to 8.0 with sodium hydroxide solution, organic facies is collected in absolute ether extraction again, and rotation is steamed gained organic facies and removed organic solvent, obtains solid crude product；Solid crude product is placed in there-necked flask, adds the hydrochloric acid (21.7mmol) of 58ml, and agitation and dropping sodium nitrite solution 20ml (37.7mmol) in 30 minutes, temperature controls below 5 DEG C, solution is yellow, after dropping, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassium iodide+100ml water), is stirred vigorously, react 12h.Stopped reaction, adjusts pH value to 7.0 with sodium hydroxide solution, collects organic facies with absolute ether extraction, again organic facies is dried through washing, anhydrous magnesium sulfate, filtrate is collected by filtration successively, rotation is evaporated filtrate, separates with silica gel column chromatography, then carries out recrystallizing methanol, obtain 4.1g4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, productivity is 30%.
5,4,4 '-two bromo-6, the synthesis of 6 '-two iodo-di-s (1,2-phenylenediamine):
In there-necked flask, add 6.80g4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides (0.01mol) and the ethanol of 200ml, form suspension, 0 DEG C of dropping 14g sodium borohydride (0.37mol), mixture stirring reaction 20 hours under room temperature, stopped reaction, collect organic facies with absolute ether extraction, then by organic facies successively through washing, anhydrous magnesium sulfate dried, filtrate is collected by filtration, rotation is evaporated filtrate, obtain 5.49g product 4,4 '-two bromo-6,6 '-two iodo-di-s (1,2-phenylenediamine), productivity 88%.
The synthesis of 6,4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles:
In there-necked flask, addition 3.12g4,4 '-two bromo-6,6 '-two iodo-di-s (1,2-phenylenediamine) (5mmol) and the ethanol of 60ml, backflow, drip 1.17gSeO2(10.5mmol) aqueous solution (hot water 22ml), reactant mixture refluxes 2 hours, and stopped reaction filters, obtains 3.48g product 4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles, productivity 90%.
Two, compound 4,9-bis-bromo-6,7-bis-synthesis of (3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole):
Addition 3.87g4 in there-necked flask, 4 '-two bromo-6,6 '-two iodo-2,1,3 selenoles (5mmol), 3.07g2,6,13, (synthetic method is with reference to Chem.Commun. for 17-tetramethyl-9-octadecyne (10mmol), 2011,47,8850-8852) and 25mlDMF, it is passed through nitrogen gas stirring 20min, is subsequently adding 0.907gBu3N (10mmol) and 115mgPd (OAc)2(0.5mmol), it is warming up to 130 DEG C, heats 4h, reaction is cooled to room temperature after terminating, and with dichloromethane extraction, reacted mixed liquor is collected organic facies after washing, is dried organic facies with anhydrous sodium sulfate and removes unnecessary moisture, filtrate is collected by filtration, distillation and concentration filtrate of reducing pressure, silica gel column chromatography separates, obtain 2.48g product 4,9-bis-bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productivity 60%.
Three, 4,4-dioctyl-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] synthesis of two thiophene:
Under the protection of nitrogen, adding 8.66g2,6-bis-bromo-4 in there-necked flask, 4-dioctyl-thiophene coughs up also [2,1-b；3, 4-b '] two thiophene (0.015mol) and the tetrahydrofuran solvent of 100ml, in there-necked flask, it is slowly injected into n-BuLi (about 0.03mol) solution of 12.6mL2.5M with syringe under the conditions of-78 DEG C, continue stirring reaction 2h, 8.4mL tributyltin chloride (0.03mol) is injected with syringe under the conditions of-78 DEG C, it is warmed to room temperature lower stirring reaction 6 hours, it is eventually adding 30ml saturated sodium-chloride water solution and terminates reaction, organic facies is collected with absolute ether extraction, it is dried organic facies with anhydrous sodium sulfate and removes unnecessary moisture, collected by suction filtrate rotation evaporate solvent.Finally crude product being carried out neutral alumina column chromatography for separation, obtain product 4,4-dioctyl-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] two thiophene, productivity 70%.
It is four, poly-that { 4,4-dioctyl-thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) } synthesis:
Under nitrogen protection, adding 199.4mg4,4-dioctyl-2 in there-necked flask, 6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] two thiophene (0.2mmol), 165.2mg4,9-bis-bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) (0.2mmol) and 40ml tetrahydrofuran solvent, evacuation deoxygenation is also filled with nitrogen, is subsequently adding 5mgPd (PPh3)2Cl2(7.1×10-3Mmol), 90 DEG C of reaction 72h it are heated to.After reaction, in the reaction bulb of product, mixed liquor after Stille coupled reaction adds water and toluene extracts, collect organic facies, decompression distillation and concentration organic facies is to volume about 5ml, organic facies after concentrating again joins in 400ml dehydrated alcohol, stirring, solid precipitation is had to separate out, collected by suction solid precipitation is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids of gained uses methanol sedimentation after extracting three days with acetone apparatus,Soxhlet's the most successively, under vacuum pump, sucking filtration is overnight, obtain the end-product of purification.
End-product after purifying carries out GPC test, number-average molecular weight Mn ≈ 55650, n=50, and copolymer material monodispersity is 2.4.
Embodiment 2 is poly-, and { 4,4-dimethyl-thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) }:
The preparation process of this copolymer material is as follows:
The synthesis of one, 4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles is with the step one of embodiment 1；
Two, compound 4,9-bis-bromo-6,7-bis-the synthesis of (3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) with the step 2 of embodiment 1.
Three, 4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] synthesis of two thiophene:
Under the protection of nitrogen, adding 3.80g4,4-dimethyl-2 in there-necked flask, 6-dibromo thiophene coughs up also [2,1-b；3,4-b '] two thiophene (0.01mol) and the tetrahydrofuran solvent of 40ml, in there-necked flask, it is slowly injected into n-BuLi (0.02mol) solution of 8.6mL2.5M with syringe under the conditions of-78 DEG C, continue stirring reaction 1.5h, under the conditions of-78 DEG C, inject 5.6mL tributyltin chloride (0.02mol) with syringe, after reacting 1 hour, be warming up under room temperature stirring reaction 6 hours.It is eventually adding the termination reaction of 30ml saturated sodium-chloride water solution, collects organic facies with absolute ether extraction, be dried the moisture that organic facies removing is unnecessary, collected by suction filtrate rotation with anhydrous sodium sulfate and evaporate solvent.Finally crude product is carried out neutral alumina column chromatography for separation, obtain product, productivity 65%.
It is four, poly-that { 4,4-dimethyl-thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) } synthesis:
Under nitrogen protection, adding 160mg4,4-dimethyl-2 in there-necked flask, 6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] two thiophene (0.2mmol), 160mg4,9-bis-bromo-6,7-bis-(3,7-dimethyl) octyl group-benzo [2,1-e:3,4-e] two (selenole) (0.2mmol) and 40ml tetrahydrofuran solvent, evacuation deoxygenation is also filled with nitrogen, is subsequently adding 5mgPd2(dba)3(5.5×10-3Mmol), 90 DEG C of reaction 72h it are heated to.After reaction, in the reaction bulb of product, mixed liquor after Stille coupled reaction adds water and toluene extracts, collect organic facies, decompression distillation and concentration organic facies is to volume about 5ml, organic facies after concentrating again joins in 400ml dehydrated alcohol, stirring, solid precipitation is had to separate out, collected by suction solid precipitation is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids of gained uses methanol sedimentation after extracting three days with acetone apparatus,Soxhlet's the most successively, under vacuum pump, sucking filtration is overnight, obtain the end-product of purification.
End-product after purifying carries out GPC test, number-average molecular weight Mn ≈ 19257, n=21, and copolymer material monodispersity is 2.3.
Embodiment 3 is poly-, and { 4,4-bis-(AI3-28404 base) thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) }:
The preparation process of this copolymer material is as follows:
The synthesis of one, 4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles is with the step one of embodiment 1.
The synthesis of two, 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole):
7.74g4 is added in there-necked flask, 4 '-two bromo-6,6 '-two iodo-2,1,3 selenole (10mmol), 1.36g2-pentyne (20mmol) (synthetic method with reference to Chem.Commun., 2011,47,8850-8852) and 50mlDMF, it is passed through nitrogen gas stirring 20min, adds 1.814gBu3N (20mmol) and 230mgPd (OAc)2(1.0mmol), being warming up to 130 DEG C, be cooled to room temperature after heating 4h reaction, the mixed liquor obtained collects organic facies with dichloromethane extraction after washing, the moisture removed in organic facies it is dried again with anhydrous sodium sulfate, filtrate is collected by filtration, and filtrate is crossed silica gel column chromatography after decompression distillation and concentration and is separated, and obtains 5.15g product 4,9-bis-bromo-6-methyl-7-ethyl-benzo [2,1-e:3,4-e] two (selenoles), productivity 65%.
Three, 4,4-bis-(AI3-28404 bases)-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] synthesis of two thiophene:
Under the protection of nitrogen, in there-necked flask, add 9.13g2,6-bis-bromo-4,4-bis-(AI3-28404 base)-thiophene cough up also [2,1-b；3,4-b '] two thiophene (0.01mol) and the tetrahydrofuran solvent of 90ml, it is slowly injected into 8.6mL2.5M n-BuLi (0.02mol) solution with syringe again under the conditions of-78 DEG C, continue stirring reaction 1h, under the conditions of-78 DEG C, inject 5.6mL tributyltin chloride (0.02mol) with syringe, after reacting 1 hour, be warming up under room temperature stirring reaction 6 hours.Adding 30ml saturated sodium-chloride water solution and terminate reaction, collect organic facies with absolute ether extraction, anhydrous sodium sulfate is dried and removes moisture unnecessary in organic facies, after sucking filtration, filtrate collection rotation are evaporated solvent, finally crude product is carried out neutral alumina column chromatography for separation, obtain product, productivity 72%.
It is four, poly-that { 4,4-bis-(AI3-28404 base) thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) synthesis:
Under nitrogen protection, adding 266.8mg4,4-bis-(AI3-28404 bases)-2 in there-necked flask, 6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] two thiophene (0.2mmol), 117.6mg4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) (0.2mmol) and 40ml toluene solvant, evacuation deoxygenation is also filled with nitrogen, is subsequently adding 9mgPd (PPh3)4(7.8×10-3Mmol), 90 DEG C of reaction 72h it are heated to.After reaction, in the reaction bulb of product, mixed liquor after Stille coupled reaction adds water and toluene extracts, collect organic facies, decompression distillation and concentration organic facies is to volume about 5ml, organic facies after concentrating again joins in 400ml dehydrated alcohol, stirring, solid precipitation is had to separate out, collected by suction solid precipitation is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids of gained uses methanol sedimentation after extracting three days with acetone apparatus,Soxhlet's the most successively, under vacuum pump, sucking filtration is overnight, obtain the end-product of purification.
End-product after purifying carries out GPC test, number-average molecular weight Mn ≈ 23028, n=19, and copolymer material monodispersity is 2.7.
Embodiment 4 is poly-, and { 4,4-bis-(AI3-28404 base) thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenole) }:
The preparation process of this copolymer material is as follows:
The synthesis of one, 4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles is with the step one of embodiment 1.
The synthesis of the bromo-6-of two, 4,9-bis-(2,7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (diazosulfide):
3.87g4 is added in there-necked flask, 4 '-two bromo-6,6 '-two iodo-2,1,3 selenoles (5mmol), 4.47g2, (synthetic method is with reference to Chem.Commun. for 6 dimethyl-9-30 alkynes (10mmol), 2011,47,8850-8852) and 30mlDMF, it is passed through nitrogen gas stirring 20min, adds 0.907gBu3N (10mmol) and 115mgPd (OAc)2(0.5mmol), it is warming up to 130 DEG C, after heating 4h, is cooled to room temperature, with dichloromethane extraction, reacted mixed liquor is collected organic facies after washing, and anhydrous sodium sulfate is dried and removes moisture unnecessary in organic facies, filters organic facies and collects filtrate, filtrate is crossed silica gel column chromatography after decompression distillation and concentration and is separated, obtain 2.7g product 4,9-bis-bromo-6,7-bis-(3,7-dimethyl octyl group)-benzo [2,1-e:3,4-e] two (selenoles), productivity 62%.
Three, 4,4-bis-(AI3-28404 bases)-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] synthesis of two thiophene is with the step 3 of embodiment 3.
It is four, poly-that { 4,4-bis-(AI3-28404 base) thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6-(3,7-dimethyl) octyl group-7-eicosyl-benzo [2,1-e:3,4-e] two (selenole) } synthesis:
Under nitrogen protection, adding 400.2mg4,4-bis-(AI3-28404 bases)-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] two thiophene (0.3mmol), 193.4mg4, the bromo-6-of 9-bis-(2,7-dimethyl) octyl group-7-eicosyl benzo [2,1-e:3,4-e] two (selenole) (0.2mmol) and 40ml glycol dinitrate ether solvents, evacuation deoxygenation is also filled with nitrogen, is subsequently adding 28.04mgPd (PPh3)2Cl2(0.04mmol) 120 DEG C of reaction 100h, it are heated to.After reaction, in the reaction bulb of product, mixed liquor after Stille coupled reaction adds water and toluene extracts, collect organic facies, decompression distillation and concentration organic facies is to volume about 5ml, organic facies after concentrating again joins in 400ml dehydrated alcohol, stirring, solid precipitation is had to separate out, collected by suction solid precipitation is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids of gained uses methanol sedimentation after extracting three days with acetone apparatus,Soxhlet's the most successively, under vacuum pump, sucking filtration is overnight, obtain the end-product of purification.
End-product after purifying carries out GPC test, number-average molecular weight Mn ≈ 159000, n=100, and copolymer material monodispersity is 6.0.
Embodiment 5 is poly-, and { 4,4-dimethyl-thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) }:
The synthesis of one, 4,4 '-two bromo-6,6 '-two iodo-2,1,3-selenoles is with the step one of embodiment 1.
The synthesis of two, 4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) is with embodiment 3.
Three, 4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] synthesis of two thiophene is with the step 3 of embodiment 2.
It is four, poly-that { 4,4-dimethyl-thiophene coughs up also [2,1-b；3,4-b '] two thiophene-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) synthesis:
Under nitrogen protection, adding 160mg4,4-dimethyl-2,6-bis-(tributyl tin)-thiophene coughs up also [2,1-b；3,4-b '] two thiophene (0.2mmol), 176.4mg4,9-bis-bromo-6-methyl-7-ethyl benzo [2,1-e:3,4-e] two (selenole) (0.3mmol) and 40ml benzene solvent, evacuation deoxygenation is also filled with nitrogen, is subsequently adding 1.05mgPd (PPh3)2Cl2(1.5×10-4Mmol) 50 DEG C of reaction 6h it are heated to.After reaction, in the reaction bulb of product, mixed liquor after Stille coupled reaction adds water and toluene extracts, collect organic facies, decompression distillation and concentration organic facies is to volume about 5ml, organic facies after concentrating again joins in 400ml dehydrated alcohol, stirring, solid precipitation is had to separate out, collected by suction solid precipitation is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids of gained uses methanol sedimentation after extracting three days with acetone apparatus,Soxhlet's the most successively, under vacuum pump, sucking filtration is overnight, obtain the end-product of purification.
End-product after purifying carries out GPC test, number-average molecular weight Mn ≈ 679, n=1.
Embodiment 6
The copolymer material prepared with embodiment 1-3, as active layer, prepares polymer solar cell device, and its structure is as it is shown in figure 1, include substrate, anode, middle auxiliary layer, active layer and the negative electrode stacked gradually.Wherein, substrate is glass.Anode be square resistance be the tin indium oxide (ITO) of 10 Ω/mouth.Middle auxiliary layer uses poly-(3,4-ethylenedioxy siloledithiophene-bepreparationothiadiazmethod): polystyrolsulfon acid composite (is called for short PEDOT:PSS).Active layer includes electron donor material and electron acceptor material, and electron donor material is copolymer material prepared by embodiment 1-3, and electron acceptor material is [6,6] phenyl-C61-methyl butyrate (being called for short PCBM).Negative electrode is aluminum.This device architecture i.e. can be briefly described as glass/ITO/PEDOT:PSS/ active layer/Al；Wherein, brace "/" is layer structure, lower same.
Wherein, substrate of glass, as bottom, chooses ito glass (with the glass of anode ITO layer) during making, thickness is 1.1mm, after ultrasonic waves for cleaning, processes with oxygen-Plasma；Then the middle auxiliary layer PEDOT:PSS of coating on ito glass, thickness is 120nm；Again copolymer material prepared by 10mg embodiment 1-3 being dissolved in 0.4ml dimethylbenzene, be dissolved in, with 8mgPCBM, the solution blending that 0.4ml chlorobenzene obtains, be spun on PEDOT:PSS film layer, thickness is about 150nm, obtains active layer；At vacuum condition (2 × 10-3Pa) evaporation cathode metallic aluminium under, thickness is 120nm, obtains polymer solar cell device.
All preparation process are all carried out in the glove box providing the inert protective gas atmosphere such as nitrogen.
By Keithley236 current/voltage source-measurement system and the I-E characteristic of the polymer solar cell device testing above-mentioned preparation, the performance data obtaining device is shown in Table 1.
The performance data of the polymer solar cell device that the copolymer material that table 1 is prepared with embodiment 1-3 is prepared for active layer
As seen from the data in Table 1, the energy conversion efficiency preparing the polymer solar cell device that copolymer material is prepared as active layer by embodiment 1-3 is 1.03～1.98, show containing siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material due to containing new benzo two (selenole) conjugate unit, high with the matching degree of solar spectrum, it it is planar conjugate structure simultaneously, carrier mobility speed is high, carrier can be improved and arrive ratio and the charge collection efficiency of electrode, thus improve energy conversion efficiency, and by the improvement of device architecture or modification, higher energy conversion efficiency can be obtained.
Embodiment 7
With embodiment 1 preparation copolymer material 1 as luminescent layer, prepare organic electroluminescence device, its structure is as in figure 2 it is shown, include glass substrate, transparent anode, luminescent layer, cushion and the negative electrode stacked gradually.Wherein, transparent anode is the tin indium oxide that square resistance is 10 Ω/mouth (ITO) of thickness 150nm, luminescent layer is the copolymer material of embodiment 1 preparation of 90nm thickness, cushion is 1.5nmLiF, reality is cathode buffer layer, negative electrode is the metal Al of 150nm, and the structure of device is represented by: glass/ITO/ luminescent layer/cushion/Al.
Measured system (Keithley2400Sourcemeter) by Keithley source and test the current versus brightness-voltage characteristic of above-mentioned organic electroluminescence device, with JY company of France its electroluminescent spectrum of SPEXCCD3000 spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency recording organic electroluminescence device is 13.9cd/A, and high-high brightness is 1188cd/m2。
Being appreciated that in other embodiments, the structure of solar cell device and organic electroluminescence device is not limited to described in above-described embodiment 6 and 7.
Embodiment described above only have expressed the several embodiments of the present invention, and it describes more 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, it is also possible to make some deformation and improvement, these broadly fall into 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. siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material, structural formula is:
Wherein, R1、R2、R3And R4For C1～C20Alkyl；N is the integer between 1～100.
2. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material, it is characterised in that comprise the steps:
Thering is provided compound A and compound B, the structural formula of described compound A is:
The structural formula of described compound B is:
R1、R2、R3And R4For C1～C20Alkyl；
In inert protective gas atmosphere; by compound A and compound B according to the ratio that mol ratio is 1:1.5～1.5:1; in catalysts and solvents, carry out Stille coupled reaction, isolated and purified after obtain described siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material that structural formula is following:
N is the integer between 1～100.
3. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material as claimed in claim 2, it is characterised in that described catalyst is Pd2(dba)3、Pd(PPh3)2Cl2Or Pd (PPh3)4；The consumption of described catalyst is the 0.05%～20% of compound A mole.
4. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material as claimed in claim 2, it is characterised in that described solvent is oxolane, glycol dimethyl ether, benzene or toluene.
5. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material as claimed in claim 2, it is characterised in that the purification procedures of described siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material is:
Mixed liquor after Stille coupled reaction adds water and toluene extracts, collect organic facies, organic facies described in decompression distillation and concentration, described organic facies after concentrating again joins in dehydrated alcohol, stirring, solid precipitation is had to separate out, solid precipitation described in collected by suction is also dried, the solids chloroform obtained crosses neutral alumina chromatographic column after dissolving, collect solution, decompression removes solvent unnecessary in solution, carry out methanol sedimentation the most successively, sucking filtration, the solids acetone apparatus,Soxhlet's of gained carries out methanol sedimentation after extracting the most successively, sucking filtration, obtain described siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material of purification.
6. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material as claimed in claim 2, it is characterised in that described compound A is made by the steps and obtains:
There is provided and there is the compound C of following structural formula:
R3And R4For C1～C20Alkyl；
In inert protective gas atmosphere; under the conditions of-78 DEG C; it is the ratio of 1:2 by described compound C and n-BuLi according to mol ratio; reaction 1～2 hour in a solvent, then adds tributyltin chloride in reacted mixed liquor, is warming up to room temperature reaction 6 hours after continuing to react 1 hour under the conditions of-78 DEG C; add saturated sodium-chloride water solution and terminate reaction; obtaining described compound A after isolated and purified, wherein, the mole of described tributyltin chloride is 2 times of described compound C mole.
7. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material as claimed in claim 6, it is characterised in that the purification procedures of described compound A is:
Absolute ether extraction is added in reacted mixed liquor, collect organic facies, and the moisture removed in described organic facies it is dried with anhydrous sodium sulfate, sucking filtration, collect liquid phase, described liquid phase is carried out rotary evaporation concentration, the crude product obtained is crossed neutral alumina column chromatography, obtain the described compound A of purification.
8. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material as claimed in claim 2, it is characterised in that described compound B is made by the steps and obtains:
Thering is provided compound D and compound E, wherein, the structural formula of compound D is:
The structural formula of compound E is:
R1And R2For C1～C20Alkyl；
In inert protective gas atmosphere, in the mixed solution of compound D and compound E, add Bu3N and Pd (OAc)2Carry out ring closure reaction, isolated and purified after obtain described compound B, wherein, the mol ratio of compound D and compound E is 1:2, and the solvent in mixed solution is dimethylformamide, Bu3The mol ratio of N and compound E is 1:1, Pd (OAc)2Mole is compound D mole 10%.
9. the preparation method of siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material as claimed in claim 8, it is characterised in that the purification procedures of described compound B is:
Use water and dichloromethane to extract reacted mixed liquor, collect organic facies, and be dried the moisture removed in described organic facies with anhydrous sodium sulfate, filter, collect liquid phase, the excess of solvent that decompression is distilled off in described liquid phase, cross silica gel column chromatography, obtain the described compound B of purification.
10. siloledithiophene-bepreparationothiadiazmethod-benzo two (selenole) copolymer material application in polymer solar cell device, organic electroluminescence device, organic field effect tube, organic light storage device, organic non-linear optical properties and organic laser apparatus as claimed in claim 1.
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