CN103833988B - Also two (diazosulfide) copolymer and its preparation method and application is coughed up containing anthracene-thiophene - Google Patents
Also two (diazosulfide) copolymer and its preparation method and application is coughed up containing anthracene-thiophene Download PDFInfo
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Abstract
The present invention relates to cough up also two (diazosulfide) copolymer and its preparation method and application containing anthracene-thiophene.A kind of cough up and two (diazosulfide) copolymer containing anthracene-thiophene, there is following structural formula:Wherein, n is the integer of 1 ~ 100；R1、R2For C1~C20Alkyl；R3、R4For H, C1~C20Alkyl or C1~C20Alkoxyl.Above-mentioned cough up containing anthracene-thiophene and two (diazosulfide) copolymer has the strongest donor-receiver structure, on the one hand be conducive to improve and cough up containing anthracene-thiophene and the stability of two (diazosulfide) copolymer, on the other hand advantageously reduce and cough up and the band gap of two (diazosulfide) copolymer containing anthracene-thiophene, thus expand sunlight absorption region, improve electricity conversion.
Description
Technical field
The present invention relates to field of photoelectric material, particularly relate to a kind of anthracene-thiophene that contains and cough up also two (diazosulfide) copolymer and its preparation method and application.
Background technology
High efficiency solar cell is typically with inorganic semiconductor as raw material, but main silicon wafer solaode is complicated due to production process technology, seriously polluted, and power consumption is big, and cost is high, it is suppressed that the development of its commercial applications.Prepare low cost hence with cheap material, dynamical solaode is always study hotspot and the difficult point of photovoltaic art.Organic semiconducting materials on the one hand owing to the environmental stability of organic material is good, synthesis low cost, that function is prone to modulation, pliability and film property is preferable；On the other hand relatively easy due to the organic solar batteries course of processing, can low-temperature operation, the advantages such as element manufacturing cost is relatively low and receive much concern, become the most cheap and attractive solar cell material.In addition, the potential advantages of organic solar batteries also include: can realize large area manufacture, can use flexible substrate, environmental friendliness, light portable etc..
Diazosulfide unit has the reduction reversibility of excellence, with the work function value of the metallic cathode such as magnesium, aluminum closely；Belong to short of electricity subtype aromatic cycle compound, there is strong electron-withdrawing power, be a kind of excellent to be there is by body unit preferable electronic transport property, the energy gap of material can also be regulated simultaneously.But, the band gap (energy level difference between HOMO energy level and lumo energy) of the existing polymer containing diazosulfide unit is wider, reduce the absorbance of photon in solar spectral, so that the energy conversion efficiency of the organic solar batteries of the polymer that use is containing connection thiazole unit is relatively low.
Summary of the invention
Based on this, it is necessary to provide a kind of energy conversion efficiency that can improve solar cell device coughs up also two (diazosulfide) copolymer and its preparation method and application containing anthracene-thiophene.
A kind of cough up and two (diazosulfide) copolymer containing anthracene-thiophene, there is following structural formula:
Wherein, n is the integer of 1 ~ 100；R1、R2For C1~C20Alkyl；R3、R4For H, C1~C20Alkyl or C1~C20Alkoxyl.
A kind of preparation method coughing up also two (diazosulfide) copolymer containing anthracene-thiophene, comprises the steps:
Thering is provided compound A and compound B, the structural formula of compound A is:
Wherein, R1、R2For C1~C20Alkyl；
The structural formula of compound B is:
Wherein, R3、R4For H, C1~C20Alkyl or C1~C20Alkoxyl；
Under anaerobic state, it is that 1:1.5 ~ 1.5:1 compound A and compound B carries out Suzuki coupled reaction in the organic solvent of the aqueous solution containing organic palladium catalyst and alkali by mol ratio, wherein, described catalyst is 1:2000 ~ 1:5 with the mol ratio of described compound A, in the aqueous solution of described alkali, the mole of alkali is 2 ~ 20 times of compound B, obtain after isolated and purified coughing up and two (diazosulfide) copolymer containing anthracene-thiophene, described cough up containing anthracene-thiophene and the general molecular formula of two (diazosulfide) copolymer is:
Wherein, n is the integer of 1 ~ 100.
In a preferred embodiment, described isolated and purified step is:
In reaction system, add toluene and deionized water extracts, take organic facies, at least part of solvent of described organic facies is removed by the method for decompression distillation, again described organic facies is added dropwise to precipitating in absolute methanol, pressed powder is obtained after sucking filtration, drying, again described pressed powder chloroform is dissolved, chromatographic column is crossed with silica gel, remove chloroform, again use methanol precipitating, again use methanol precipitating after the solid acetone extraction obtained after filtration, after filtration, be dried to obtain coughing up and two (diazosulfide) copolymer containing anthracene-thiophene after purification.
In a preferred embodiment, the reaction temperature of described Suzuki coupled reaction is 50 DEG C ~ 120 DEG C, and the response time is 6 hours ~ 100 hours.
In a preferred embodiment, at least one in oxolane, glycol dimethyl ether, benzene and toluene of described organic solvent, at least one in potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate and potassium bicarbonate of described alkali.
In a preferred embodiment, described compound A adopts and prepares with the following method:
Compound C and compound D that following structural formula represents are provided,
C is:D is:Wherein R1、R2For C1~C20Alkyl；
Under anaerobic reaction condition, in compound C, inject DMF, under-90 ° of C, be slowly added to n-BuLi, stirring reaction 2 hours, wherein n-BuLi is x, 2≤x 4 with the mol ratio of compound C, is subsequently adding compound D, react 10 hours after being warmed up to room temperature, isolated and purified obtaining described compound A, wherein, the mol ratio of compound D and compound C is 2:1.
In a preferred embodiment, described isolated and purified obtain described compound A step be:
After reaction terminates, water wash, extract with absolute ether, organic layer anhydrous sodium sulfate is dried, after filtration, decompression is distilled off solvent, the compound A after the purification of recycle silicon glue chromatographic column isolated.
In a preferred embodiment, described compound B adopts and prepares with the following method:
Compound E and compound F that following structural formula represents are provided,
E is:F is:Wherein R3、R4For H, C1~C20Alkyl or C1~C20Alkoxyl；
Under anhydrous and oxygen-free reaction condition, tetrahydrofuran solvent is injected in compound E, it is slowly added to n-BuLi under-78 ° of C, stirring reaction 2 hours, wherein compound E is 1:2 with the mol ratio of n-BuLi, then slowly injects compound F at-78 DEG C, react 6 hours after being warmed up to room temperature after reacting 1 hour, isolated and purified obtaining described compound B, wherein, the mol ratio of compound F and compound E is 2:1.
In a preferred embodiment, described isolated and purified obtain described compound B step be:
After reaction terminates, add saturated NaCl solution and terminate reaction, use absolute ether extraction, re-use anhydrous Na2SO4It is dried organic facies, collects filtrate after sucking filtration, obtain crude product after removing solvent, described crude product is carried out silica gel column chromatography separation, the compound B after being purified.
Above-mentioned cough up and the application in solar cell device and organic electroluminescence device of two (diazosulfide) copolymer containing anthracene-thiophene.
Above-mentioned cough up and two (diazosulfide) copolymer and preparation method thereof containing anthracene-thiophene, compound anthracene and thiophene are coughed up and two (diazosulfides) carry out copolymerization, benzo two (diazosulfide) has simple in construction, symmetrical, the advantages such as electron delocalization performance is good, and there is planar structure, it it is the most excellent a kind of acceptor material, obtain cough up containing anthracene-thiophene and two (diazosulfide) copolymer has the strongest donor-receiver structure, on the one hand be conducive to improve and cough up containing anthracene-thiophene and the stability of two (diazosulfide) copolymer, on the other hand advantageously reduce and cough up and the band gap of two (diazosulfide) copolymer containing anthracene-thiophene, thus expand sunlight absorption region, improve electricity conversion.
Accompanying drawing explanation
Fig. 1 is coughing up and two (diazosulfide) copolymer preparation method flow chart containing anthracene-thiophene of an embodiment；
Fig. 2 is for coughing up containing anthracene-thiophene and two (diazosulfide) copolymer is as the structural representation of the organic solar batteries device of active layer material；
Fig. 3 is for coughing up containing anthracene-thiophene and two (diazosulfide) copolymer is as the structural representation of the organic electroluminescence device of emitting layer material.
Detailed description of the invention
Understandable for enabling the above-mentioned purpose of the present invention, feature and advantage to become apparent from, below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in detail.Elaborate a lot of detail in the following description so that fully understanding the present invention.But the present invention can implement to be much different from alternate manner described here, those skilled in the art can do similar improvement in the case of intension of the present invention, and therefore the present invention is not limited by following public being embodied as.
Coughing up and two (diazosulfide) copolymer containing anthracene-thiophene of one embodiment, has a following structural formula:
Wherein, n is the integer of 1 ~ 100；R1、R2For C1~C20Alkyl；R3、R4For H, C1~C20Alkyl or C1~C20Alkoxyl.
Above-mentioned cough up and two (diazosulfide) copolymer containing anthracene-thiophene, compound anthracene and thiophene are coughed up and two (diazosulfides) carry out copolymerization, benzo two (diazosulfide) has simple in construction, symmetrical, the advantages such as electron delocalization performance is good, and there is planar structure, it it is the most excellent a kind of acceptor material, obtain cough up containing anthracene-thiophene and two (diazosulfide) copolymer has the strongest donor-receiver structure, on the one hand be conducive to improve and cough up containing anthracene-thiophene and the stability of two (diazosulfide) copolymer, on the other hand advantageously reduce and cough up and the band gap of two (diazosulfide) copolymer containing anthracene-thiophene, thus expand sunlight absorption region, improve electricity conversion.
Refer to Fig. 1, coughing up containing anthracene-thiophene and the preparation method of two (diazosulfide) copolymer of an embodiment, comprise the steps:
Step S110, offer compound A and compound B.The structural formula of compound A is:
Wherein, R1、R2For C1~C20Alkyl；
The structural formula of compound B is:
Wherein, R3、R4For H, C1~C20Alkyl or C1~C20Alkoxyl；
Step S120, under anaerobic state, it is that 1:1.5 ~ 1.5:1 compound A and compound B carries out Suzuki coupled reaction in the organic solvent of the aqueous solution containing organic palladium catalyst and alkali by mol ratio, wherein, catalyst is 1:2000 ~ 1:5 with the mol ratio of compound A, in the aqueous solution of alkali, the mole of alkali is 2 ~ 20 times of compound B, obtain after isolated and purified coughing up and two (diazosulfide) copolymer containing anthracene-thiophene, cough up containing anthracene-thiophene and the general molecular formula of two (diazosulfide) copolymer is:
Wherein, n is the integer of 1 ~ 100；
The reaction equation of this step is:
Preferably, Na2CO3The concentration of aqueous solution is 2mol/L.
Preferably, at least one in oxolane, glycol dimethyl ether, benzene and toluene of organic solvent.
Preferably, organic palladium catalyst is selected from three (dibenzalacetone) two palladium (Pd2(dba)3), tetrakis triphenylphosphine palladium (Pd (PPh3)4) and two (triphenylphosphine) palladium chloride (Pd (PPh3)2Cl2At least one in).It should be noted that catalyst is not limited to above-mentioned several catalyst, other organic palladium catalyst can also, as long as can catalytic cpd A and compound B react.
Preferably, the reaction temperature of Suzuki coupled reaction is 50 DEG C ~ 120 DEG C, and the response time is 6 hours ~ 100 hours.
Preferably, at least one in potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate and potassium bicarbonate of alkali.
Preferably, purification procedures in the step s 120 is:
In reaction system, add toluene and deionized water extracts, take organic facies, at least part of solvent of described organic facies is removed by the method for decompression distillation, again described organic facies is added dropwise to precipitating in absolute methanol, pressed powder is obtained after sucking filtration, drying, again described pressed powder chloroform is dissolved, chromatographic column is crossed with silica gel, remove chloroform, again use methanol precipitating, again use methanol precipitating after the solid acetone extraction obtained after filtration, after filtration, be dried to obtain coughing up and two (diazosulfide) copolymer containing anthracene-thiophene after purification.
In step s 110, compound A can be by being purchased or preparing.Preferably, compound A can adopt and prepare with the following method:
Step S111, provide compound C and compound D that following structural formula represents,
C is:D is:Wherein R1、R2For C1~C20Alkyl.
Step S112, under anaerobic reaction condition, in compound C, inject DMF, under-90 ° of C, be slowly added to n-BuLi, stirring reaction 2 hours, wherein n-BuLi is x, 2≤x 4 with the mol ratio of compound C, is subsequently adding compound D, react 10 hours after being warmed up to room temperature, isolated and purified obtaining described compound A, wherein, the mol ratio of compound D and compound C is 2:1.
The reaction equation of this step is as follows:
Preferably, in course of reaction, reaction system is passed through nitrogen or argon.
Preferably, reaction is carried out under conditions of anhydrous and oxygen-free.
Preferably, the purification procedures in step S112 is:
After reaction terminates, water wash, extract with absolute ether, organic layer anhydrous sodium sulfate is dried, after filtration, decompression is distilled off solvent, the compound A after the purification of recycle silicon glue chromatographic column isolated.
Wherein the preparation of compound C comprises the following steps:
Step one, by 2-amino-5-nitroaniline add thionyl chloride (SOCl2In), drip pyridine while stirring, the wherein ratio of 2-amino-5-nitroaniline and the amount that solid-to-liquid ratio is 6:1(material of pyridine), it is heated to 80 DEG C ~ 90 DEG C back flow reaction afterwards 24 hours, remove the thionyl chloride of excess afterwards, after cooling, add deionized water precipitating, collect solid washing final vacuum and be dried to obtain 5-nitro-2,1,3 diazosulfide.
The reaction equation of this step is:
Step 2, by 5-nitro-2, 1, reflux at 127 DEG C after 3 diazosulfides and hydrobromic acid solution mixing, to 5-nitro-2, 1, the mixed liquor formed after 3 diazosulfides and hydrobromic acid solution mixing drips bromine, back flow reaction 4 hours, heat filtering afterwards, refilter after filtrate is cooled down, it is dried after the solids washed with water obtained, 4 are obtained the most successively with glacial acetic acid and Gossypol recrystallized from chloroform, 7-bis-bromo-5-nitro-2, 1, 3 diazosulfides, wherein, hydrobromic mass concentration is 40%, 5-nitro-2, 1, 3 diazosulfides and mass concentration be the hydrobromic ratio of 40% be 4mol:1L, 5-nitro-2, 1, 3 diazosulfides are 60mol:11.3L with the ratio of bromine.
The reaction equation of this step is:
Step 3, it is the 4 of 102:95 by mass ratio, 7-bis-bromo-5-nitro-2,1,3 diazosulfides and copper powder add DMF (DMF), react 3 hours at 120 DEG C, add toluene agitation and filtration after being cooled down by reactant liquor, filtrate is washed with aqueous solution and the water of saturated sodium chloride, merges organic facies, anhydrous magnesium sulfate is dried, filter, revolve be evaporated, dehydrated alcohol recrystallization, obtain 4,4 '-two bromo-6,6 '-dinitro-connection 2,1,3 diazosulfide.
The reaction equation of this step is:
Preferably, 4,7-bis-bromo-5-nitro-2,1,3 diazosulfide is 1:1 with the volume ratio that solid-to-liquid ratio is 1mol:3L, DMF and toluene of DMF.
Step 4, by 4,4 '-two bromo-6,6 '-dinitros that mol ratio is 1:10-join 2,1,3 diazosulfides and SnCl2Add oxolane (THF), it is warming up to 100 DEG C, back flow reaction 10 hours, sodium hydroxide solution is used to regulate the pH value of reactant liquor to 8 after cooling, use absolute ether extraction afterwards, collect organic facies and remove organic solvent therein and obtain solid crude product, after solid crude product and mixed in hydrochloric acid, dropping sodium nitrite solution, diazo-reaction is carried out 30 minutes below 5 DEG C, reactant liquor is added dropwise in liquor kalii iodide, it is stirred vigorously reaction 12 hours, then with sodium hydroxide solution, the pH value of reactant liquor is regulated to 7, extract with absolute ether, wash after collecting organic facies, filter, remove the organic solvent in filtrate afterwards, separate with silica gel column chromatography, again with methanol is recrystallized to give compound C(4, 4 '-two bromo-6, 6 '-two iodo-2, 1, 3 diazosulfides):
Preferably, 4,4 '-two bromo-6,6 '-dinitro-connection 2,1,3 diazosulfide is 20:21.7 with the mol ratio of hydrochloric acid, 4,4 '-two bromo-6,6 '-dinitro-connection 2,1,3 diazosulfide is 20:37.7 with the mol ratio of sodium nitrite, 4,4 '-two bromo-6,6 '-dinitro-connection 2,1,3 diazosulfide is 10.3:62 with the mass ratio of potassium iodide.
In step S111, compound B can be by being purchased or preparing.Preferably, described compound B adopts and prepares with the following method:
Step S121, provide compound E and compound F that following structural formula represents,
E is:F is:Wherein R3、R4For H, C1~C20Alkyl or C1~C20Alkoxyl.
Step S122, under anhydrous and oxygen-free reaction condition, tetrahydrofuran solvent is injected in compound E, it is slowly added to n-BuLi under-78 ° of C, stirring reaction 2 hours, wherein compound E is 1:2 with the mol ratio of n-BuLi, then slowly injects compound F at-78 DEG C, react 6 hours after being warmed up to room temperature after reacting 1 hour, isolated and purified obtaining described compound B, wherein, the mol ratio of compound F and compound E is 2:1.
The reaction equation of this step is:
In step S122, isolated and purified obtain compound B step be:
After reaction terminates, add saturated NaCl solution and terminate reaction, use absolute ether extraction, re-use anhydrous Na2SO4It is dried organic facies, collects filtrate after sucking filtration, obtain crude product after removing solvent, described crude product is carried out silica gel column chromatography separation, the compound B after being purified.
Further illustrate below by way of specific embodiment.
Embodiment 1
The polymer P 1 that the open structure of the present embodiment is following:
The preparation process of P1 is as follows:
Step one, the preparation 1 of 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides, 5-nitro-2, the preparation of 1,3 diazosulfide:
In there-necked flask, add 2-amino-5-nitroaniline (22.95g, 0.15mol) and 100ml thionyl chloride, stirring slowly dropping 2ml pyridine, in 80 ~ 90 DEG C of back flow reaction 24h, stopped reaction after heating, be heated to 80 DEG C of rotations and steam the SOCl of excess2After, product is cooled to room temperature, is poured in a large amount of water, stir, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productivity 80%.
2,4,7-bis-bromo-5-nitro-2, the preparation of 1,3 diazosulfide:
5-nitro-2,1,3 diazosulfide (10.35g is added in there-necked flask, 60mmol) and the hydrobromic acid 15ml of 40%, it is warming up to 127 DEG C of backflows, in 30min, slowly drips bromine 11.3ml the 4h that refluxes, heat filtering, refilter after filtrate cooling, solid washs with substantial amounts of water and is dried, with glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 10.2g, productivity: 50%.
3,4,4 '-two bromo-6, the preparation of 6 '-dinitro-connection 2,1,3 diazosulfide:
Addition 4 in there-necked flask, 7-bis-bromo-5-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g, the DMF (DMF) of 90ml, after being heated to 120 DEG C of reactions 3 hours, stopped reaction, is cooled to room temperature, adds 90ml toluene, stir 30 minutes, filter, filtrate saturated aqueous common salt and water washing, merging organic layer, anhydrous magnesium sulfate is dried, and filters, rotation is evaporated, dehydrated alcohol recrystallization, obtains product 4, and 4 '-two bromo-6,6 '-dinitro-connection 2,1,3 diazosulfide 4.7g, productivity 30.2%.
The preparation of 4,4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides:
In there-necked flask, add 4, 4 '-two bromo-6, 6 '-dinitro-connection 2, 1, 3 diazosulfide (10.3g, 20mmol), add the oxolane (THF) that 300ml is dried, add 40gSnCl2 (200mmol), it is warming up to 100 DEG C, it is heated to reflux 10h, stopped reaction, cooling, adjust pH value to 8.0 with sodium hydroxide solution, absolute ether extracts, gained organic layer is steamed in rotation, obtain solid crude product, it is put in there-necked flask, add the hydrochloric acid (21.7mmol) of 58ml, agitation and dropping sodium nitrite solution 20ml(37.7mmol in 30 minutes), temperature controls below 5 DEG C, solution is yellow, after dropping, react 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, extracts with absolute ether, organic layer is washed, and anhydrous magnesium sulfate is dried, and filters, 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%.
Step 2,4,8-bis-bromo-6,6-dioctyl-thiophene coughs up also the preparation of [3,2-e:4,5-e] two (diazosulfide):
4,4 '-two bromo-6,6 '-two iodo-2 are added in there-necked flask, 1,3 diazosulfide (3.4g, 5mmol), 50mlDMF, is passed through nitrogen gas stirring 20min, slowly drips n-BuLi (6mL, 2.5M, 0.015mol), half an hour, drips off, control temperature and be-90 DEG C, stir 2 hours at being maintained at-90 DEG C, add 4.73ml dioctyl dichlorosilane (10mmol), it is warmed to room temperature, stirring reaction 10 hours.Stopped reaction, washing, absolute ether extracts, obtains organic layer, and anhydrous sodium sulfate is dried, filtering, decompression distillation, silica gel column chromatography separates, obtains 4.43g product 4,8-bis-bromo-6,6-dioctyl-thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide), productivity 65%.
Step 3,2,6-dioctyl-9, the preparation of 10-bis-(4,4,5,5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene:
Under the protection of nitrogen; 2 are added in there-necked flask; 6-dioctyl-9; 10-dibromoanthracene (5.60g, 0.01mol), adds the tetrahydrofuran solvent of 60ml; slowly inject n-BuLi (8mL again with syringe under the conditions of-78 DEG C; 2.5M, 0.02mol), continue stirring reaction 2h; 2-isopropoxy-4 is injected with syringe under the conditions of-78 DEG C; 4,5,5-tetramethyls-1; 3; 2-di (hetero) oxygen pentaborane (4.3mL, 0.02mol), is warming up under room temperature stirring reaction 6 hours after reacting 1 hour.Adding saturated sodium-chloride water solution (30ml) and terminate reaction, extract with absolute ether, anhydrous sodium sulfate is dried, and after filtering, filtrate collection rotation is evaporated solvent.Finally crude product is carried out silica gel column chromatography separation, obtain product, productivity 92%.
Step 4, poly-the preparation of { 2,6-dioctyl anthracene-6,6 dioctyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) }:
Under nitrogen protection, 2 are added, 6-dioctyl-9; 10-bis-(4,4,5; 5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene (131mg; 0.2mmol), 6,6-dioctyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (136.2mg, 0.2mmol) and toluene 40ml; evacuation deoxygenation is also filled with nitrogen, is subsequently adding (5mg, 0.0043mmol) Pd (PPh3)4, 1mlNa2CO3(2M, 2mmol), is heated to 90 DEG C of reaction 90h.After reaction, in the reaction bulb of product, add deionized water and toluene extracts, take organic facies, by the method for decompression distillation, polymer/toluene solution is evaporated to about about 5ml, it is added dropwise in 400ml dehydrated alcohol be stirred continuously, there is solid precipitation to separate out, after sucking filtration, drying, obtain pressed powder.Being dissolved by pressed powder chloroform, cross chromatographic column with silica gel, decompression removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Polymer (P1) after purifying carries out GPC test, number-average molecular weight Mn ≈ 52360, n=55, and polymer monodispersity is 2.6.
Embodiment 2
The polymer P 2 that the open structure of the present embodiment is following:
The preparation process of P2 is as follows:
Step one, the preparation of 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides
Step one with embodiment 1.
Step 2,4,8-bis-bromo-6,6-dioctyl-thiophene coughs up also the preparation of [3,2-e:4,5-e] two (diazosulfide)
Step 2 with embodiment 1.
Step 3,2,6-bis-octyloxy-9, the preparation of 10-bis-(4,4,5,5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene:
Under the protection of nitrogen; 2 are added in there-necked flask; 6-bis-octyloxy-9; 10-dibromoanthracene (5.92g, 0.01mol), adds the tetrahydrofuran solvent of 60ml; slowly inject n-BuLi (8mL again with syringe under the conditions of-78 DEG C; 2.5M, 0.02mol), continue stirring reaction 2h; 2-isopropoxy-4 is injected with syringe under the conditions of-78 DEG C; 4,5,5-tetramethyls-1; 3; 2-di (hetero) oxygen pentaborane (4.3mL, 0.02mol), is warming up under room temperature stirring reaction 6 hours after reacting 1 hour.Adding saturated sodium-chloride water solution (30ml) and terminate reaction, extract with absolute ether, anhydrous sodium sulfate is dried, and after filtering, filtrate collection rotation is evaporated solvent.Finally crude product is carried out silica gel column chromatography separation, obtain product, productivity 93%.
Step 4, the preparation of poly-{ 2,6-bis-octyloxy anthracene-6,6 dioctyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) }:
Under nitrogen protection, 2 are added, 6-bis-octyloxy-9; 10-bis-(4,4,5; 5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene (137.4mg; 0.2mmol), 6,6-dioctyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (136.2mg, 0.2mmol) and oxolane 40ml; evacuation deoxygenation is also filled with nitrogen, is subsequently adding (5mg, 0.0043mmol) Pd (PPh3)4, 1mlK2CO3(2M, 2mmol), is heated to 100 DEG C of reaction 24h.After reaction, in the reaction bulb of product, add deionized water and toluene extracts, take organic facies, by the method for decompression distillation, polymer/toluene solution is evaporated to about about 5ml, it is added dropwise in 400ml dehydrated alcohol be stirred continuously, there is solid precipitation to separate out, after sucking filtration, drying, obtain pressed powder.Being dissolved by pressed powder chloroform, cross chromatographic column with silica gel, decompression removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Polymer (P2) after purifying carries out GPC test, number-average molecular weight Mn ≈ 48216, n=49, and polymer monodispersity is 2.5.
Embodiment 3
The polymer P 3 that the open structure of the present embodiment is following:
Step one, the preparation of 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides
Step one with embodiment 1.
Step 2,4,8-bis-bromo-6,6-dimethyl-thiophene coughs up also the preparation of [3,2-e:4,5-e] two (diazosulfide):
4,4 '-two bromo-6,6 '-two iodo-2 are added in there-necked flask, 1,3 diazosulfide (3.4g, 5mmol), 50mlDMF, is passed through nitrogen gas stirring 20min, slowly drips n-BuLi (4mL, 2.5M, 0.01mol), half an hour, drips off, control temperature and be-90 DEG C, stir 2 hours at being maintained at-90 DEG C, add 4.73ml dimethyldichlorosilane (10mmol), it is warmed to room temperature, stirring reaction 10 hours.Stopped reaction, washing, absolute ether extracts, obtains organic layer, and anhydrous sodium sulfate is dried, filtering, decompression distillation, silica gel column chromatography separates, obtains 3.38g product 4,8-bis-bromo-6,6-dimethyl-thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide), productivity 70%.
Step 3,2,6-bis-(AI3-28404 epoxide)-9, the preparation of 10-bis-(4,4,5,5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene:
Under the protection of nitrogen; 2 are added in there-necked flask; 6-bis-(AI3-28404 epoxide)-9; 10-dibromoanthracene (9.29g, 0.01mol), adds the tetrahydrofuran solvent of 100ml; slowly inject n-BuLi (15.2mL again with syringe under the conditions of-78 DEG C; 2.5M, 0.38mol), continue stirring reaction 1.5h; 2-isopropoxy-4 is injected with syringe under the conditions of-78 DEG C; 4,5,5-tetramethyls-1; 3; 2-di (hetero) oxygen pentaborane (4.3mL, 0.02mol), is warming up under room temperature stirring reaction 6 hours after reacting 1 hour.Adding saturated sodium-chloride water solution (30ml) and terminate reaction, extract with absolute ether, anhydrous sodium sulfate is dried, and after filtering, filtrate collection rotation is evaporated solvent.Finally crude product is carried out silica gel column chromatography separation, obtain product, productivity 94%.
Step 4, the preparation of poly-{ 2,6-bis-(AI3-28404 epoxide) anthracene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) }:
Under nitrogen protection, 2 are added, 6-bis-(AI3-28404 epoxide)-9; 10-bis-(4,4,5; 5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene (204.6mg; 0.2mmol), 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (96.8mg, 0.2mmol) and glycol dinitrate ether solvents 40ml; evacuation deoxygenation is also filled with nitrogen, is subsequently adding (5mg, 0.0055mmol) Pd2(dba)3, 1mlCs2CO3(2M, 2mmol), is heated to 90 DEG C of reaction 72h.After reaction, in the reaction bulb of product, add deionized water and toluene extracts, take organic facies, by the method for decompression distillation, polymer/toluene solution is evaporated to about about 5ml, it is added dropwise in 400ml dehydrated alcohol be stirred continuously, there is solid precipitation to separate out, after sucking filtration, drying, obtain pressed powder.Being dissolved by pressed powder chloroform, cross chromatographic column with silica gel, decompression removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Polymer (P3) after purifying carries out GPC test, number-average molecular weight Mn ≈ 28100, n=25, and polymer monodispersity is 2.7.
Embodiment 4
The polymer P 4 that the open structure of the present embodiment is following:
Step one, the preparation of 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides
Step one with embodiment 1.
Step 2,4,8-bis-bromo-6,6-dioctyl-thiophene coughs up also the preparation of [3,2-e:4,5-e] two (diazosulfide)
Step 2 with embodiment 1.
Step 3,2,6-dimethoxy-9, the preparation of 10-bis-(4,4,5,5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene:
Under the protection of nitrogen; 2 are added in there-necked flask; 6-dimethoxy-9; 10-dibromoanthracene (3.96g, 0.01mol), adds the tetrahydrofuran solvent of 40ml; slowly inject n-BuLi (8mL again with syringe under the conditions of-78 DEG C; 2.5M, 0.02mol), continue stirring reaction 1.5h; 2-isopropoxy-4 is injected with syringe under the conditions of-78 DEG C; 4,5,5-tetramethyls-1; 3; 2-di (hetero) oxygen pentaborane (4.3mL, 0.02mol), is warming up under room temperature stirring reaction 6 hours after reacting 1 hour.Adding saturated sodium-chloride water solution (30ml) and terminate reaction, extract with absolute ether, anhydrous sodium sulfate is dried, and after filtering, filtrate collection rotation is evaporated solvent.Finally crude product is carried out silica gel column chromatography separation, obtain product, productivity 80%.
Step 4, the preparation of poly-{ 2,6-dimethoxy anthracene-6,6 dimethyl thiophenes cough up also [3,2-e:4,5-e] two (diazosulfide) }:
Under nitrogen protection, 2 are added, 6-dimethoxy-9; 10-bis-(4,4,5; 5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene (98mg; 0.2mmol), 6,6-dioctyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (136.2mg, 0.2mmol) and benzene solvent 40ml; evacuation deoxygenation is also filled with nitrogen, is subsequently adding (5mg, 0.0071mmol) Pd (PPh3)2Cl2, 1ml potassium tert-butoxide (2M, 2mmol), it is heated to 80 DEG C of reaction 48h.After reaction, in the reaction bulb of product, add deionized water and toluene extracts, take organic facies, by the method for decompression distillation, polymer/toluene solution is evaporated to about about 5ml, it is added dropwise in 400ml dehydrated alcohol be stirred continuously, there is solid precipitation to separate out, after sucking filtration, drying, obtain pressed powder.Being dissolved by pressed powder chloroform, cross chromatographic column with silica gel, decompression removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Polymer after purifying carries out GPC test, number-average molecular weight Mn ≈ 22036, n=28, and polymer monodispersity is 3.2.
Embodiment 5
The polymer P 5 that the open structure of the present embodiment is following:
Step one, 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides preparation with the step one of embodiment 1.
Step 2 ,-4,8-bis-bromo-6,6-bis-(AI3-28404 base) thiophene coughs up also the preparation of [3,2-e:4,5-e] two (diazosulfide):
4,4 '-two bromo-6,6 '-two iodo-2 are added in there-necked flask, 1,3 diazosulfide 5mmol, 50mlDMF, it is passed through nitrogen gas stirring 20min, slowly drips n-BuLi (10.9mL, 2.5M, 0.0195mol), half an hour, drips off, and controls temperature and is-90 DEG C, stir 2 hours at being maintained at-90 DEG C, add 9.86ml bis-(AI3-28404 base) dichlorosilane (20mmol), be warmed to room temperature, stirring reaction 10 hours.Stopped reaction, washing, absolute ether extracts, obtains organic layer, and anhydrous sodium sulfate is dried, filtering, decompression distillation, silica gel column chromatography separates, obtains 2.79g product 4,8-bis-bromo-6,6-bis-(AI3-28404 base)-thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide), productivity 55%.
Step 3,9, the preparation of 10-bis-(4,4,5,5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene:
Under the protection of nitrogen; 9 are added in there-necked flask; 10-dibromoanthracene (3.36g; 0.01mol); add the tetrahydrofuran solvent of 40ml, under the conditions of-78 DEG C, slowly inject n-BuLi (12mL, 2.5M again with syringe; 0.03mol); continue stirring reaction 1.5h, with syringe injection 2-isopropoxy-4 under the conditions of-78 DEG C, 4; 5; 5-tetramethyl-1,3,2-di (hetero) oxygen pentaborane (4.3mL; 0.02mol), reaction is warming up under room temperature stirring reaction 6 hours after 1 hour.Adding saturated sodium-chloride water solution (30ml) and terminate reaction, extract with absolute ether, anhydrous sodium sulfate is dried, and after filtering, filtrate collection rotation is evaporated solvent.Finally crude product is carried out silica gel column chromatography separation, obtain product, productivity 80%.
Step 4, the preparation of poly-{ anthracene-6,6-bis-(AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) }:
Under nitrogen protection, 9 are added, 10-bis-((4; 4,5,5-tetramethyls-1; 3,2-di (hetero) oxygen pentaboranes) anthracene (86mg, 0.2mmol), 6; 6-dioctyl-4,8-dibromo thiophene coughs up also [3,2-e:4; 5-e] two (diazosulfide) (136.2mg, 0.2mmol) and toluene solvant 40ml, evacuation deoxygenation is also filled with nitrogen; it is subsequently adding (5mg, 0.0043mmol) Pd (PPh3)4, 1ml sodium tert-butoxide (2M, 2mmol), it is heated to 70 DEG C of reaction 56h.After reaction, in the reaction bulb of product, add deionized water and toluene extracts, take organic facies, by the method for decompression distillation, polymer/toluene solution is evaporated to about about 5ml, it is added dropwise in 400ml dehydrated alcohol be stirred continuously, there is solid precipitation to separate out, after sucking filtration, drying, obtain pressed powder.Being dissolved by pressed powder chloroform, cross chromatographic column with silica gel, decompression removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Polymer after purifying carries out GPC test, number-average molecular weight Mn ≈ 23408, n=22, and polymer monodispersity is 3.0.
Embodiment 6
The polymer P 6 that the open structure of the present embodiment is following:
Step one, the preparation of 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides
Step one with embodiment 1.
Step 2,4,8-bis-bromo-6,6-bis-(AI3-28404 base)-thiophene coughs up also the preparation of [3,2-e:4,5-e] two (diazosulfide)
Step 2 with embodiment 5.
Step 3,2,6-bis-(AI3-28404 base)-9, the preparation of 10-bis-(4,4,5,5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene:
Under the protection of nitrogen; 2 are added in there-necked flask; 6-bis-(AI3-28404 base)-9; 10-dibromoanthracene (8.97g, 0.01mol), adds the tetrahydrofuran solvent of 90ml; slowly inject n-BuLi (8mL again with syringe under the conditions of-78 DEG C; 2.5M, 0.02mol), continue stirring reaction 1.5h; 2-isopropoxy-4 is injected with syringe under the conditions of-78 DEG C; 4,5,5-tetramethyls-1; 3; 2-di (hetero) oxygen pentaborane (4.3mL, 0.02mol), is warming up under room temperature stirring reaction 6 hours after reacting 1 hour.Adding saturated sodium-chloride water solution (30ml) and terminate reaction, extract with absolute ether, anhydrous sodium sulfate is dried, and after filtering, filtrate collection rotation is evaporated solvent.Finally crude product is carried out silica gel column chromatography separation, obtain product, productivity 90%.
Step 4, the preparation of poly-{ 2,6-bis-(AI3-28404 base) anthracene-6,6-bis-(AI3-28404 base) thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) }:
Under nitrogen protection; add 2; 6-bis-(AI3-28404 base)-9; 10-bis-(4,4,5; 5-tetramethyl-1; 3,2-di (hetero) oxygen pentaboranes) anthracene (297.3mg, 0.3mmol), 6; 6-bis-(AI3-28404 base)-4; 8-dibromo thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) (203.4mg; 0.2mmol) with toluene solvant 40ml; evacuation deoxygenation is also filled with nitrogen, is subsequently adding (46.16mg, 0.0399mmol) Pd (PPh3)4, 3ml sodium bicarbonate (2M, 6mmol), it is heated to 120 DEG C of reaction 100h.After reaction, in the reaction bulb of product, add deionized water and toluene extracts, take organic facies, by the method for decompression distillation, polymer/toluene solution is evaporated to about about 5ml, it is added dropwise in 400ml dehydrated alcohol be stirred continuously, there is solid precipitation to separate out, after sucking filtration, drying, obtain pressed powder.Being dissolved by pressed powder chloroform, cross chromatographic column with silica gel, decompression removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Polymer after purifying carries out GPC test, number-average molecular weight Mn ≈ 162500, n=100, and polymer monodispersity is 4.8.
Embodiment 7
The polymer P 7 that the open structure of the present embodiment is following:
Step one, the preparation of 4,4 '-two bromo-6,6 '-two iodo-2,1,3 diazosulfides
Step one with embodiment 1.
Step 2,4,8-bis-bromo-6,6-dimethyl-thiophene coughs up also the preparation of [3,2-e:4,5-e] two (diazosulfide)
Step 2 with embodiment 3.
Step 3,2,6-dimethyl-9, the preparation of 10-bis-(4,4,5,5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene:
Under the protection of nitrogen; 2 are added in there-necked flask; 6-dimethyl-9; 10-dibromoanthracene (3.64g, 0.01mol), adds the tetrahydrofuran solvent of 40ml; slowly inject n-BuLi (16mL again with syringe under the conditions of-78 DEG C; 2.5M, 0.04mol), continue stirring reaction 1.5h; 2-isopropoxy-4 is injected with syringe under the conditions of-78 DEG C; 4,5,5-tetramethyls-1; 3; 2-di (hetero) oxygen pentaborane (4.3mL, 0.02mol), is warming up under room temperature stirring reaction 6 hours after reacting 1 hour.Adding saturated sodium-chloride water solution (30ml) and terminate reaction, extract with absolute ether, anhydrous sodium sulfate is dried, and after filtering, filtrate collection rotation is evaporated solvent.Finally crude product is carried out silica gel column chromatography separation, obtain product, productivity 87%.
Step 4, the preparation of poly-{ 2,6-dimethylanthracene-6,6-dimethyl thiophene coughs up also [3,2-e:4,5-e] two (diazosulfide) }:
Under nitrogen protection, 2 are added, 6-dimethyl-9; 10-bis-(4,4,5; 5-tetramethyl-1,3,2-di (hetero) oxygen pentaboranes) anthracene (91.6mg; 0.2mmol), 6,6-dimethyl-4,8-dibromo thiophene coughs up also [3; 2-e:4,5-e] two (diazosulfide) (145.2mg, 0.3mmol) and toluene solvant 40ml; evacuation deoxygenation is also filled with nitrogen, is subsequently adding (0.17mg, 0.000147mmol) Pd (PPh3)4, 0.2ml potassium bicarbonate (2M, 0.4mmol), it is heated to 50 DEG C of reaction 6h.After reaction, in the reaction bulb of product, add deionized water and toluene extracts, take organic facies, by the method for decompression distillation, polymer/toluene solution is evaporated to about about 5ml, it is added dropwise in 400ml dehydrated alcohol be stirred continuously, there is solid precipitation to separate out, after sucking filtration, drying, obtain pressed powder.Being dissolved by pressed powder chloroform, cross chromatographic column with neutral alumina, decompression removes organic solvent, and methanol settles.Sucking filtration, gained solid acetone apparatus,Soxhlet's extracts three days.Methanol settles, sucking filtration.It is pumped through under vacuum pump and obtains product night.
Polymer after purifying carries out GPC test, number-average molecular weight Mn ≈ 559, n=1.
Embodiment 8
To cough up containing anthracene-thiophene and two (diazosulfide) copolymer p prepares organic solar batteries device as active layer 14 electron donor material, its structure such as Fig. 2.Organic solar batteries device includes the substrate of glass 11 stacked gradually, anode 12, middle auxiliary layer 13, active layer 14 and negative electrode 15.Anode 12 is ITO, be square resistance be the tin indium oxide of 10-20 Ω/mouth, middle auxiliary layer 13 uses poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid composite, is called for short PEDOT:PSS(CLEVIOSPVPA14083)；Active layer 14 includes electron donor material and electron acceptor material, and electron donor material is polymer prepared by the embodiment of the present invention, and electron acceptor material is [6,6] phenyl-C61-methyl butyrate (being called for short PCBM)；Negative electrode 15 is aluminum, i.e. this device architecture can be briefly described as its structure and is: glass/ITO/PEDOT:PSS/P:PCBM/Al.
Wherein, substrate of glass 11, as bottom, chooses ito glass (with anode 12ITO layer, commercially available) during making, thickness is 1.1mm, after ultrasonic waves for cleaning, processes with oxygen-Plasma；Then the middle auxiliary layer 13 of coating on ito glass, material is PEDOT:PSS, and thickness is 120nm；Again copolymer prepared by the 10mg embodiment of the present invention 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 100nm, obtains active layer 14；At vacuum condition (2 × 10-3Pa) evaporation cathode 15 under, material is aluminum, and thickness is 120nm, obtains organic solar batteries device.Preparation method and the structure of the organic solar batteries device containing present copolymer are not limited to the present embodiment, can be suitably modified device or modify.
The copolymer (being respectively adopted P1 ~ P3 to replace) embodiment 1 ~ 3 prepared respectively uses said method to prepare organic solar batteries device.The electrical property of organic solar batteries device, i.e. I-E characteristic, obtained by Keithley236 current/voltage source-measurement system and test device detection, be shown in Table 1.
Table 1
As seen from the data in Table 1, the energy conversion efficiency of the organic solar batteries that the copolymer prepared by the present invention is prepared as active layer is 0.91 ~ 1.31, these show coughing up and two (diazosulfides) of the present invention containing anthracene-thiophene } copolymer is owing to coughing up and two (diazosulfide) conjugate unit containing new thiophene, 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 9
With embodiment 1 preparation copolymer p 1 as emitting layer material, prepare organic electroluminescence device, its structure is as it is shown on figure 3, include the glass substrate 21 stacked gradually, transparent anode 22, luminescent layer 23, cushion 24 and negative electrode 25.Wherein, transparent anode 22 is tin indium oxide (ITO) (150nm) that square resistance is 10-20 Ω/mouth, luminescent layer 23 is the copolymer p 1(100nm of the embodiment of the present invention 1 preparation), cushion 24 is LiF (1.5nm), negative electrode 25 is metal Al (150nm), the structure of device is: glass/ITO/ copolymer 1/LiF/Al, but the structure of practical devices is not limited to this.
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 15.6cd/A, and high-high brightness is 1170cd/m2。
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 (9)
1. cough up and two (diazosulfide) copolymer containing anthracene-thiophene for one kind, it is characterised in that there is following structural formula:
Wherein, n is the integer of 1～100；R1、R2For C1～C20Alkyl；R3、R4For H, C1～C20Alkyl or C1～C20Alkoxyl.
2. cough up and the preparation method of two (diazosulfide) copolymer containing anthracene-thiophene for one kind, it is characterised in that comprise the steps:
Thering is provided compound A and compound B, the structural formula of compound A is:
Wherein, R1、R2For C1～C20Alkyl；
The structural formula of compound B is:
Wherein, R3、R4For H, C1～C20Alkyl or C1～C20Alkoxyl；
Under anaerobic state, it is that 1:1.5～1.5:1 compound A and compound B carries out Suzuki coupled reaction in the organic solvent of the aqueous solution containing organic palladium catalyst and alkali by mol ratio, wherein, described catalyst is 1:2000～1:5 with the mol ratio of described compound A, in the aqueous solution of described alkali, the mole of alkali is 2～20 times of compound B, obtain after isolated and purified coughing up and two (diazosulfide) copolymer containing anthracene-thiophene, described cough up containing anthracene-thiophene and the general molecular formula of two (diazosulfide) copolymer is:
Wherein, n is the integer of 1～100, and the reaction temperature of described Suzuki coupled reaction is 50 DEG C～120 DEG C, and the response time is 6 hours～100 hours.
The preparation method coughing up also two (diazosulfide) copolymer containing anthracene-thiophene the most according to claim 2, it is characterised in that described isolated and purified step is:
In reaction system, add toluene and deionized water extracts, take organic facies, at least part of solvent of described organic facies is removed by the method for decompression distillation, again described organic facies is added dropwise to precipitating in absolute methanol, pressed powder is obtained after sucking filtration, drying, again described pressed powder chloroform is dissolved, chromatographic column is crossed with silica gel, remove chloroform, again use methanol precipitating, again use methanol precipitating after the solid acetone extraction obtained after filtration, after filtration, be dried to obtain coughing up and two (diazosulfide) copolymer containing anthracene-thiophene after purification.
The preparation method coughing up also two (diazosulfide) copolymer containing anthracene-thiophene the most according to claim 2, it is characterized in that, at least one in oxolane, glycol dimethyl ether, benzene and toluene of described organic solvent, at least one in potassium carbonate, cesium carbonate, potassium tert-butoxide, sodium tert-butoxide, sodium carbonate, sodium bicarbonate and potassium bicarbonate of described alkali.
The preparation method coughing up also two (diazosulfide) copolymer containing anthracene-thiophene the most according to claim 2, it is characterised in that described compound A adopts and prepares with the following method:
Compound C and compound D that following structural formula represents are provided,
C is:D is:Wherein R1、R2For C1～C20Alkyl；
Under anaerobic reaction condition, in compound C, inject DMF, at-90 DEG C, be slowly added to n-BuLi, stirring reaction 2 hours, wherein n-BuLi is x, 2≤x 4 with the mol ratio of compound C, is subsequently adding compound D, react 10 hours after being warmed up to room temperature, isolated and purified obtaining described compound A, wherein, the mol ratio of compound D and compound C is 2:1.
The most according to claim 5 cough up and the preparation method of two (diazosulfide) copolymer containing anthracene-thiophene, it is characterised in that described isolated and purified obtain described compound A step be:
After reaction terminates, water wash, extract with absolute ether, organic layer anhydrous sodium sulfate is dried, after filtration, decompression is distilled off solvent, the compound A after the purification of recycle silicon glue chromatographic column isolated.
The preparation method coughing up also two (diazosulfide) copolymer containing anthracene-thiophene the most according to claim 2, it is characterised in that described compound B adopts and prepares with the following method:
Compound E and compound F that following structural formula represents are provided,
E is:F is:Wherein R3、R4For H, C1～C20Alkyl or C1～C20Alkoxyl；
Under anhydrous and oxygen-free reaction condition, tetrahydrofuran solvent is injected in compound E, it is slowly added to n-BuLi at-78 DEG C, stirring reaction 2 hours, wherein compound E is 1:2 with the mol ratio of n-BuLi, then slowly injects compound F at-78 DEG C, react 6 hours after being warmed up to room temperature after reacting 1 hour, isolated and purified obtaining described compound B, wherein, the mol ratio of compound F and compound E is 2:1.
The most according to claim 7 cough up and the preparation method of two (diazosulfide) copolymer containing anthracene-thiophene, it is characterised in that described isolated and purified obtain described compound B step be:
After reaction terminates, add saturated NaCl solution and terminate reaction, use absolute ether extraction, re-use anhydrous Na2SO4It is dried organic facies, collects filtrate after sucking filtration, obtain crude product after removing solvent, described crude product is carried out silica gel column chromatography separation, the compound B after being purified.
9. anthracene-the thiophene that contains as claimed in claim 1 is coughed up and the application in solar cell device and organic electroluminescence device of two (diazosulfide) copolymer.
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| CN101501862A (en) * | 2005-07-14 | 2009-08-05 | 科纳卡技术股份有限公司 | Polymers with low band gaps and high charge mobility |
| CN102105511A (en) * | 2008-08-11 | 2011-06-22 | 三菱化学株式会社 | Charge-transporting polymer, composition for organic electroluminescent element, organic electroluminescent element, organic EL display device and organic EL illuminating device |
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| CN101501862A (en) * | 2005-07-14 | 2009-08-05 | 科纳卡技术股份有限公司 | Polymers with low band gaps and high charge mobility |
| CN102105511A (en) * | 2008-08-11 | 2011-06-22 | 三菱化学株式会社 | Charge-transporting polymer, composition for organic electroluminescent element, organic electroluminescent element, organic EL display device and organic EL illuminating device |
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