CN103833967A - 1,8-carbazole-silolodi(benzothiadiazole)-containing copolymer, preparation method and application thereof - Google Patents
1,8-carbazole-silolodi(benzothiadiazole)-containing copolymer, preparation method and application thereof Download PDFInfo
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- 0 C*C=C(C1)C=Cc(c2ccc3)c1[n](*1CC1)c2c3-c1cc([Si-]c2c-3c4n[s]nc4c(C(C)(C)N)c2)c-3c2n[s]nc12 Chemical compound C*C=C(C1)C=Cc(c2ccc3)c1[n](*1CC1)c2c3-c1cc([Si-]c2c-3c4n[s]nc4c(C(C)(C)N)c2)c-3c2n[s]nc12 0.000 description 4
- RATMDCXCCVYJTG-UHFFFAOYSA-N Brc1cc([SiH+]c2c-3c4n[s]nc4c(Br)c2)c-3c2n[s]nc12 Chemical compound Brc1cc([SiH+]c2c-3c4n[s]nc4c(Br)c2)c-3c2n[s]nc12 RATMDCXCCVYJTG-UHFFFAOYSA-N 0.000 description 1
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Abstract
The present invention relates to a 1,8-carbazole-silolodi(benzothiadiazole)-containing copolymer, a preparation method and an application thereof. The 1,8-carbazole-silolodi(benzothiadiazole)-containing copolymer has the following structural formula, wherein n is an integer of 1-100, and R1, R2 and R3 are C1-C20 alkyl. According to the present invention, the polymer formed by 1,8-carbazole and silolodi(benzothiadiazole) can form a strong donor-acceptor structure, such that the stability of the material can be easily increased, and the band gap of the material can be easily reduced so as to expand the light-absorbing range of the material and improve the photoelectric conversion efficiency.
Description
Technical field
The present invention relates to photoelectron material field, particularly relate to and a kind of coughing up and the multipolymer of two (diazosulfides) and its preparation method and application containing 1,8-carbazole-thiophene.
Background technology
The solar cell that preparation cost is low, usefulness is high is study hotspot and the difficult point in photovoltaic field always.Business-like silicon solar cell, because complex manufacturing, cost are high, is restricted its application at present.
In order to reduce costs, expand range of application, people are finding novel solar cell material always for a long time.Polymer solar battery has superior market outlook because the mode big area such as cheap, the quality of cost of material is light, flexibility, simple, the available coating of production technique, printing such as prepare at the advantage.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C
60between Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed.At present the effciency of energy transfer of polymer solar battery is still low than silicon solar cell, one of reason be due to the carrier mobility of polymkeric substance than the mobility of inorganic monocrystal material low several orders of magnitude.The absorption spectrum of the conjugated polymers photocell material using at present can not mate well with solar spectrum, is another major reason that causes energy transfer efficiency low.
Summary of the invention
Based on this, be necessary to provide a kind of effciency of energy transfer higher coughing up and the multipolymer of two (diazosulfides) and its preparation method and application containing 1,8-carbazole-thiophene.
A kind of 1,8-carbazole-thiophene that contains is coughed up the also multipolymer of two (diazosulfides), has following structural formula:
Wherein, the integer that n is 1 ~ 100; R
1, R
2, R
3for C
1~ C
20alkyl.
A kind of 1,8-carbazole-thiophene that contains is coughed up the also preparation method of the multipolymer of two (diazosulfides), comprises the steps:
Compd A and compd B are provided, and the structural formula of compd A is:
Wherein, R
1, R
2for C
1~ C
20alkyl;
The structural formula of compd B is:
Wherein, R
3for C
1~ C
20alkyl;
Under the atmosphere of rare gas element, by compd A, compd B at catalyzer, solvent and Na
2cO
3under the condition existing, carry out Suzuki coupling reaction, wherein, the mol ratio of compd A and compd B is 1:1.5 ~ 1.5:1, temperature of reaction is 50 ° of C ~ 120 ° C, time is 6 ~ 100 hours, after separation and purification, obtain having coughing up and the multipolymer of two (diazosulfides) containing 1,8-carbazole-thiophene of following structural formula:
Wherein, the integer that n is 1 ~ 100.
In a preferred embodiment, described catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, 0.05% ~ 20% of the molar weight that the consumption of catalyzer is compd A; Described solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene;
The step of described separation and purification is:
In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again described organic phase is splashed into precipitating in anhydrous methanol, suction filtration, after oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, remove catalyzer with neutral alumina chromatography column, finally remove chloroform, methyl alcohol sedimentation, suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's, methyl alcohol sedimentation, suction filtration, under vacuum pump, taking out spends the night after being purified containing 1, 8-carbazole-thiophene is coughed up the also multipolymer of two (diazosulfides).
In a preferred embodiment, described compd A is adopted preparation with the following method:
Compound C and Compound D are provided, and the structural formula of Compound C is:
The structural formula of Compound D is:
Under anhydrous and oxygen-free reaction conditions, Compound C is dissolved in to enough N, dinethylformamide (DMF), slowly drips n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of Compound C and n-Butyl Lithium is 1:2 ~ 1:4, then under-90 ° of C, slowly inject Compound D, react 10 hours after being warmed up to room temperature, after stopped reaction, washing, anhydrous diethyl ether extraction, gets organic phase, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains described compd A, wherein, the mol ratio of Compound D and Compound C is 1:2.
In a preferred embodiment, described Compound C is adopted preparation with the following method:
Compd E is provided, and the structural formula of compd E is:
Compd E is dissolved in tetrahydrofuran (THF) (THF), adds SnCl
2, be warming up to 100 ℃, reflux 10 hours, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolve and steam gained organic layer, obtain solid crude product, add hydrochloric acid, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 ℃, after dropwising, react 30 minutes, then reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, react 12 hours, stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extract with anhydrous diethyl ether, washing organic layer, use anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness filtrate, separate with silica gel column chromatography, then carry out recrystallizing methanol, obtain Compound C.
In a preferred embodiment, described compd E is adopted preparation with the following method:
By bromo-4,7-bis-5-nitro-2,1,3 diazosulfides, copper powder, DMF mixes, be heated to 120 ℃ of reactions after 3 hours, be cooled to room temperature, add toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains compd E.
In a preferred embodiment, described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide is adopted preparation with the following method:
By 5-nitro-2, the Hydrogen bromide that 1,3 diazosulfide and mass concentration are 40% mixes, be warming up to 127 ℃ of backflows, in 30 minutes, slowly drip bromine and reflux 4 hours, heat filtering, after filtrate is cooling, refilter, wash solid dry with water, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide.
In a preferred embodiment, described 5-nitro-2,1,3 diazosulfide is adopted preparation with the following method:
2-amino-5-N-methyl-p-nitroaniline and thionyl chloride are mixed, stir and slowly drip pyridine, after heating in 80 ~ 90 ℃ of back flow reaction 24 hours, stopped reaction, is heated to 80 ℃ and revolves and steam after excessive thionyl chloride, and reaction product is cooled to room temperature, after stirring in the large water gaging of impouring, filtering, wash final vacuum is dried, obtain 5-nitro-2,1,3 diazosulfide.
In a preferred embodiment, described compd B is adopted preparation with the following method:
Compound F 17-hydroxy-corticosterone is provided, and the structural formula of compound F 17-hydroxy-corticosterone is:
Under atmosphere of inert gases, compound F 17-hydroxy-corticosterone is dissolved in to tetrahydrofuran (THF), at-78 ℃, slowly add n-Butyl Lithium, wherein, the mol ratio of compound F 17-hydroxy-corticosterone and n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2 hour, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-, 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, 2 times of the molar weight that the molar weight of the assorted oxygen pentaboranes of 2-bis-is compound F 17-hydroxy-corticosterone, continue at-78 ℃, to react 1 hour, then be warming up to room temperature, react 6 hours, add saturated sodium-chloride water solution termination reaction, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate solvent, finally carry out silica gel column chromatography separation, obtain described compd B.
Above-mentionedly contain that 1,8-carbazole-thiophene is coughed up and the multipolymer of two (diazosulfides) application in polymer solar cell device, organic electroluminescence device, organic field effect tube, organic optical storage and organic laser.
By 1, the polymkeric substance that 8-carbazole and thiophene are coughed up and two (diazosulfide) forms can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, thereby expand the light abstraction width of this material, improved electricity conversion.
Accompanying drawing explanation
Fig. 1 is that 1, the 8-carbazole-thiophene that contains of an embodiment is coughed up the also multipolymer preparation method schema of two (diazosulfides);
Fig. 2 is the structural representation of the organic solar batteries device of an embodiment;
Fig. 3 is the structural representation of the organic electroluminescence device of an embodiment.
Embodiment
For above-mentioned purpose of the present invention, feature and advantage can be become apparent more, below in conjunction with accompanying drawing, the specific embodiment of the present invention is described in detail.A lot of details are set forth in the following description so that fully understand the present invention.But the present invention can implement to be much different from alternate manner described here, and those skilled in the art can do similar improvement without prejudice to intension of the present invention in the situation that, and therefore the present invention is not subject to the restriction of following public concrete enforcement.
As previously mentioned, in order further to improve the performance of polymer solar battery, can adopt the utmost point narrow band gap polymkeric substance having compared with wide absorption spectrum to do to body and acceptor on the one hand, raising absorbs sun power, can adopt on the other hand annealing, add the materials such as tensio-active agent to be optimized device.
Diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the metallic cathode such as magnesium, aluminium; Belonging to short of electricity subtype aromatic cycle compound, have strong electron-withdrawing power, is that a kind of good body unit that is subject to has good electronic transport property, can also regulate the energy gap of material simultaneously.
Thiophene is coughed up and has been formed σ
*-π
*conjugation, makes thiophene cough up the minimum not occupied orbital of molecule (lowestunocccupied molecular orbital, LUMO) lower, has good electron affinity and electronic mobility simultaneously.Thiophene is coughed up and two (diazosulfides) have narrow band gap and strong conjugated nature, can be applied in the fields such as organic solar batteries.Carbazole is a good hole transport unit, is easy to modify, and has advantages of good thermostability containing carbazole polymer in conjunction with the N atom of carbazole.At present in the photoelectric material such as widespread use and Organic Light Emitting Diode, organic solar batteries, field-effect transistor.
But, containing that 1,8-carbazole-thiophene is coughed up and the polymkeric substance of two (diazosulfide) multipolymer does not still have document and patent report at present simultaneously, this has just limited its range of application greatly.
1, the 8-carbazole-thiophene that contains of one embodiment is coughed up the also multipolymer of two (diazosulfides), has following structural formula:
Wherein, the integer that n is 1 ~ 100; R
1, R
2, R
3for C
1~ C
20alkyl.The introducing of alkyl can improve solvability and the molecular weight of polymkeric substance, is conducive to film forming processing.
Thiophene is coughed up and two (diazosulfides) are a kind of very excellent donor materials, thiophene is coughed up and two (diazosulfides) have simple in structure, symmetrical, the advantages such as electron delocalization performance is good, and there is two dimensional structure, it is a kind of very excellent acceptor material, by 1, the polymkeric substance that 8-carbazole and thiophene are coughed up and two (diazosulfide) forms can form a kind of very strong donor-receiver structure, be conducive to improve on the one hand the stability of material, be conducive on the other hand reduce the band gap of material, thereby expand the absorption region of this material, improve electricity conversion.
Just because of this, above-mentionedly contain that 1,8-carbazole-thiophene is coughed up and the multipolymer of two (diazosulfides) can be applied in the fields such as polymer solar cell device, organic electroluminescence device, organic field effect tube, organic optical storage and organic laser.
Refer to Fig. 1,1, the 8-carbazole-thiophene that contains of an embodiment is coughed up the also preparation method of the multipolymer of two (diazosulfides), comprises the steps:
Step S110, provide compd A and compd B.The structural formula of compd A is:
Wherein, R
1, R
2for C
1~ C
20alkyl.
The structural formula of compd B is:
Wherein, R
3for C
1~ C
20alkyl.
Step S120, under the atmosphere of rare gas element, by compd A, compd B at catalyzer, solvent and Na
2cO
3under the condition existing, carry out Suzuki coupling reaction, wherein, the mol ratio of compd A and compd B is 1:1.5 ~ 1.5:1, temperature of reaction is 50 ° of C ~ 120 ° C, time is 6 ~ 100 hours, after separation and purification, obtain having coughing up and the multipolymer of two (diazosulfides) containing 1,8-carbazole-thiophene of following structural formula:
Wherein, the integer that n is 1 ~ 100.
The reaction formula of this step is:
Preferably, the atmosphere of rare gas element comprises nitrogen, argon gas etc.
Preferably, catalyzer is organic palladium catalyzer, for example Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2, be preferably Pd (PPh
3)
4.Being appreciated that catalyzer also can be other can catalytic cpd A and the catalyzer that reacts of compd B.
Preferably, 0.05% ~ 20% of the molar weight that the consumption of catalyzer is compd A.
Preferably, solvent can be tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene etc.The amount of solvent is enough.
Preferably, Na
2cO
3add-on be compd B 2 ~ 20 times.
Preferably, the purification procedures in step S120 is:
In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again organic phase is splashed into precipitating in anhydrous methanol, suction filtration, after oven dry, obtain pressed powder, again pressed powder is dissolved with chloroform, remove catalyzer with neutral alumina chromatography column, finally remove chloroform, methyl alcohol sedimentation, suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's, methyl alcohol sedimentation, suction filtration, under vacuum pump, taking out spends the night after being purified containing 1, 8-carbazole-thiophene is coughed up the also multipolymer of two (diazosulfides).
In step S110, compd A can be adopted preparation with the following method:
Step S111, provide Compound C and Compound D, the structural formula of Compound C is:
The structural formula of Compound D is:
Wherein, R
1, R
2for C
1~ C
20alkyl.
Step S112, under anhydrous and oxygen-free reaction conditions, Compound C is dissolved in to enough DMF, slowly drip n-Butyl Lithium (t-BuLi), stirring reaction 2 hours, wherein the mol ratio of Compound C and n-Butyl Lithium is 1:2 ~ 1:4, then under-90 ° of C with slowly injecting Compound D, react 10 hours after being warmed up to room temperature, washing, anhydrous diethyl ether extraction, gets organic phase, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains described compd A, wherein, the mol ratio of Compound D and Compound C is 1:2.
The reaction formula of this step is as follows:
In step S111, Compound C can be adopted preparation with the following method:
Step S121, provide compd E, the structural formula of compd E is:
Step S122, compd E is dissolved in dry THF, adds SnCl
2, be warming up to 100 ℃, reflux 10 hours, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolve and steam gained organic layer, obtain solid crude product, add hydrochloric acid, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 ℃, after dropwising, react 30 minutes, then reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, react 12 hours, stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extract with anhydrous diethyl ether, washing organic layer, use anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness filtrate, separate with silica gel column chromatography, then carry out recrystallizing methanol, obtain Compound C.
The reaction equation of this step is:
In step S121, compd E can be adopted preparation with the following method:
Step S131, by bromo-4,7-bis-5-nitro-2,1,3 diazosulfides, copper powder, DMF mixes, be heated to 120 ℃ of reactions after 3 hours, be cooled to room temperature, add 90mL toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains compd E.
The reaction formula of this step is:
In step S131, the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfide is adopted preparation with the following method:
Step S141, by 5-nitro-2,1,3 diazosulfide mixes with the Hydrogen bromide that mass concentration is 40%, be warming up to 127 ℃ of backflows, in 30 minutes, slowly drip bromine and reflux 4 hours, heat filtering, after filtrate is cooling, refilter, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide.
In step S141,5-nitro-2,1,3 diazosulfide can be by being purchased or preparing.Preferably, adopt preparation with the following method:
Step S151, in there-necked flask, add 2-amino-5-N-methyl-p-nitroaniline and thionyl chloride, stir and slowly drip pyridine, after heating in 80 ~ 90 ℃ of back flow reaction 24 hours, being heated to 80 ℃ revolves and steams after excessive thionyl chloride, reaction product is cooled to room temperature, after stirring, filters, wash final vacuum and be dried in water, obtain 5-nitro-2,1,3 diazosulfide.
In step S110, compd B is adopted preparation with the following method:
Step S210, provide compound F 17-hydroxy-corticosterone, the structural formula of compound F 17-hydroxy-corticosterone is:
Step S220, under atmosphere of inert gases, compound F 17-hydroxy-corticosterone is dissolved in to tetrahydrofuran (THF), at-78 ℃, slowly add n-Butyl Lithium, wherein, the mol ratio of compound F 17-hydroxy-corticosterone and n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2 hour, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-, 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, 2 times of the molar weight that the molar weight of the assorted oxygen pentaboranes of 2-bis-is compound F 17-hydroxy-corticosterone, continue at-78 ℃, to react 1 hour, then be warming up to room temperature, react 6 hours, add saturated sodium-chloride water solution termination reaction, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate solvent, finally carry out silica gel column chromatography separation, obtain described compd B.
The route of above-mentioned synthetic benzo two (diazosulfide) is fairly simple and ripe, easily improves solvability and the molecular weight of product by introducing alkyl, is conducive to film forming processing; In addition, Suzuki reaction is a kind of very ripe polyreaction, and productive rate is high, and mild condition, is easy to control.
Further illustrate by specific embodiment below.
Embodiment 1
Synthesizing of poly-{ 6 dioctyl thiophenes being coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-octyl group-2,7-carbazole-6 }.
The preparation process of above-mentioned polymkeric substance is as follows:
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
1, prepare compound 5-nitro-2,1,3 diazosulfide
In there-necked flask, add 2-amino-5-N-methyl-p-nitroaniline (22.95g, 0.15mol) and 100mL thionyl chloride, stir and slowly drip 2mL pyridine, after heating, in 80 ~ 90 ℃ of back flow reaction 24 hours, stopped reaction, was heated to 80 ℃ and revolves and steam excessive SOCl
2after, reaction product is cooled to room temperature, in the large water gaging of impouring, stir, filter, wash final vacuum and be dried, obtain product 5-nitro-2,1,3 diazosulfide 21.7g, productive rate 80%.
2, prepare compound 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide
In there-necked flask, add 5-nitro-2,1,3 diazosulfide (10.35g, 60mmol) and 40% Hydrogen bromide 15mL, be warming up to 127 ℃ of backflows, in 30 minutes, slowly drip bromine 11.3mL the 4h that refluxes, heat filtering, after filtrate is cooling, refilter, a large amount of water washing dry for solid, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain product 10.2g, productive rate is 50%.
3, preparation 4,4 '-bis-is bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides
In there-necked flask, add the bromo-5-of 4,7-bis-nitro-2,1,3 diazosulfides (10.2g, 30mmol), the copper powder of 9.5g, the DMF (DMF) of 90mL, was heated to 120 ℃ of reactions after 3 hours, stopped reaction, is cooled to room temperature, adds 90mL toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains product 4, and 4 '-bis-bromo-6,6 '-dinitrobenzene-Lian 2,1,3 diazosulfide 4.7g, productive rate is 30.2%.
4, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-dinitrobenzene-Lian, 2,1,3 diazosulfides (10.3g, 20mmol), the tetrahydrofuran (THF) (THF) that 300mL is dry, 40g SnCl
2(200mmol), to reaction flask, be warming up to 100 ℃, reflux 10 hours, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolves and steams gained organic layer, obtains solid crude product, be put in there-necked flask, add the hydrochloric acid (21.7mmol) of 58mL, agitation and dropping sodium nitrite solution 20mL(37.7mmol in 30 minutes), temperature is controlled at below 5 ℃, it is yellow that solution is, and after dropwising, reacts 30 minutes.Then reacted solution is added dropwise in liquor kalii iodide (62g potassiumiodide and 100mL water), vigorous stirring, reacts 12 hours.Stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extracts with anhydrous diethyl ether, organic layer washing, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness filtrate, with silica gel column chromatography separation, then carry out recrystallizing methanol, obtain 4.1g 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides, productive rate is 30%.
Two, prepare compound 6,6-dioctyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), 50mL DMF, passes into nitrogen gas stirring 20 minutes, slowly drips n-Butyl Lithium (6.0mL, 2.5M, 0.015mol), half hour, drips off, controlling temperature is-90 ℃, remains at-90 ℃ and stirs 2 hours, adds 4.73mL dioctyl dichlorosilane (10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, washing, anhydrous diethyl ether extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains 4.43g 4,8-bis-bromo-6,6-dioctyl thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide), and productive rate is 65%.
Three, preparation 9-octyl group-1,8-bis-((4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) carbazole
Under the protection of nitrogen; in there-necked flask, add 9-octyl group-1; 8-dibromo carbazole (4.37g; 0.01mol); add the tetrahydrofuran solvent of 50mL, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8mL, 2.5M with syringe again; 0.02mol); continue stirring reaction 2 hours, under-78 ℃ of conditions, inject 2-isopropoxy-4,4 with syringe; 5; 5-tetramethyl--1, the assorted oxygen pentaborane (4.3mL of 3,2-bis-; 0.02mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.Add saturated sodium-chloride water solution (30mL) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate is 88%.
Four, preparation poly-{ 6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-dioctyl-1,8-carbazole-6 }
Under nitrogen protection, add 9-octyl group-1,8-bis-((4; 4,5,5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-)-2,7-carbazole (106.2mg; 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); vacuumize deoxygenation and be filled with nitrogen, then add (5mg, 0.0043mmol) Pd (PPh
3)
4, 1mL Na
2cO
3(2M, 2mmol), is heated to 90 ℃ of reactions 72 hours.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by the toluene solution evaporate to dryness of polymkeric substance to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
Polymkeric substance (P1) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 37260, n=45, polymkeric substance monodispersity is 2.5.
Embodiment 2
Synthesizing of poly-{ 6 dioctyl thiophenes being coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-methyl isophthalic acid, 8-carbazole-6 }.
The preparation process of above-mentioned polymkeric substance is as follows:
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step is with the step 1 of embodiment 1.
Two, prepare compound 6,6-dioctyl-4,8-dibromo thiophene is coughed up also the step 2 of this step of [3,2-e:4,5-e] two (diazosulfide) with embodiment 1.
Three, preparation 9-methyl isophthalic acid, 8-bis-((4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) carbazole
Under the protection of nitrogen; in there-necked flask, add 9-methyl isophthalic acid; 8-dibromo carbazole (3.39g; 0.01mol); add the tetrahydrofuran solvent of 40mL, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8mL, 2.5M with syringe again; 0.02mol); continue stirring reaction 1.5 hours, under-78 ℃ of conditions, inject 2-isopropoxy-4,4 with syringe; 5; 5-tetramethyl--1, the assorted oxygen pentaborane (4.3mL of 3,2-bis-; 0.02mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.Add saturated sodium-chloride water solution (30mL) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate is 80%.
Four, preparation poly-{ 6 dioctyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-methyl isophthalic acid, 8-carbazole-6 }
Under nitrogen protection, add 9-methyl isophthalic acid, 8-bis-((4; 4,5,5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) carbazole (86.6mg, 0.2mmol), 6; 6-dioctyl-4,8-dibromo thiophene is coughed up also [3,2-e:4; 5-e] two (diazosulfide) (136.2mg, 0.2mmol) and toluene solvant 40mL to reaction flask, vacuumize deoxygenation and be filled with nitrogen; then add (5mg, 0.0055mmol) Pd
2(dba)
3, 1mL Na
2cO
3(2M, 2mmol), is heated to 90 ℃ of reaction 72h.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with silica gel, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
Polymkeric substance (P2) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 23360, n=32, polymkeric substance monodispersity is 2.2.
Embodiment 3
Synthesizing of poly-{ 6 dimethyl thiophenes being coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-NSC 62789 base-1,8-carbazole-6 }.
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step is with the step 1 of embodiment 1.
Two, prepare compound 6,6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide (3.4g, 5mmol), 50mL DMF, passes into nitrogen gas stirring 20 minutes, slowly drips n-Butyl Lithium (2mL, 2.5M, 5mmol), half hour, drips off, controlling temperature is-90 ℃, remains at-90 ℃ and stirs 2 hours, adds 4.73mL dimethyldichlorosilane(DMCS) (10mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, washing, anhydrous diethyl ether extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains 3.38g product 6,6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide), and productive rate is 70%.
Three, preparation 9-NSC 62789 base-1,8-bis-((4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) carbazole
Under the protection of nitrogen; in there-necked flask, add 9-NSC 62789 base-1; 8-dibromo carbazole (6.06g; 0.01mol); add the tetrahydrofuran solvent of 60mL, under-78 ℃ of conditions, slowly inject n-Butyl Lithium (8mL, 2.5M with syringe again; 0.02mol); continue stirring reaction 1.5h, under-78 ℃ of conditions, inject 2-isopropoxy-4,4 with syringe; 5; 5-tetramethyl--1, the assorted oxygen pentaborane (4.3mL of 3,2-bis-; 0.02mol), reaction is warming up under room temperature stirring reaction after 1 hour 6 hours.Add saturated sodium-chloride water solution (30mL) termination reaction, with anhydrous diethyl ether extraction, anhydrous sodium sulfate drying, after filtering by filtrate collection and revolve and evaporate solvent.Finally crude product is carried out to silica gel column chromatography separation, obtain product, productive rate is 93%.
Four, preparation poly-{ 6 dimethyl thiophenes are coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-NSC 62789 base-1,8-carbazole-6 }
Under nitrogen protection, add 9-NSC 62789 base-1,8-bis-((4; 4,5,5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) carbazole (140mg, 0.2mmol), 6; 6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4; 5-e] two (diazosulfide) (96.8mg, 0.2mmol) and toluene solvant (40mL) be to reaction flask, and vacuumize deoxygenation and be filled with nitrogen; then add (2.8mg, 0.004mmol) Pd (PPh
3)
2cl
2, 1mL Na
2cO
3(2M, 2mmol), is heated to 90 ℃ of reactions 72 hours.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross silica gel column chromatography, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
Polymkeric substance (P3) after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 24000, n=30, polymkeric substance monodispersity is 2.3.
Embodiment 4
Synthesizing of poly-{ 6-bis-(NSC 62789 base) thiophene being coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-NSC 62789 base-1,8-carbazole-6 }
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step is with the step 1 of embodiment 1.
Two, prepare compound 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide)
In there-necked flask, add 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfide 5mmol, 50mL DMF, pass into nitrogen gas stirring 20 minutes, slowly drip n-Butyl Lithium (8mL, 2.5M, 20mmol), half hour, drips off, and controlling temperature is-90 ℃, remain at-90 ℃ and stir 2 hours, add 9.86mL bis-(NSC 62789 base) dichlorosilane (20mmol), rise to room temperature, stirring reaction 10 hours.Stopped reaction, washing, anhydrous diethyl ether extraction, obtains organic layer, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains 2.79g product 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide), and productive rate is 55%.
Three, preparation 9-NSC 62789 base-1,8-bis-((4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) carbazole
This step is with the step 3 of embodiment 3.
Four, preparation poly-{ 6-bis-(NSC 62789 base) thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-NSC 62789 base-1,8-carbazole-6 }
Under nitrogen protection; add 9-NSC 62789 base-1; 8-bis-((4; 4; 5,5-tetramethyl--1,3; the assorted oxygen pentaborane of 2-bis-) carbazole (205.5mg; 0.3mmol), 6,6-bis-(NSC 62789 base)-4,8-dibromo thiophene coughs up also [3; 2-e:4; 5-e] two (diazosulfide) (203.4mg, 0.2mmol) and toluene solvant 40mL be to reaction flask, and vacuumize deoxygenation and be filled with nitrogen; then add (46.16mg, 0.0399mmol) Pd (PPh
3)
4, 3mL Na
2cO
3(2M, 6mmol), is heated to 120 ℃ of reactions 100 hours.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross silica gel column chromatography, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 133300, n=100, polymkeric substance monodispersity is 5.0.
Embodiment 5
Synthesizing of poly-{ 6-dimethyl thiophene being coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-methyl isophthalic acid, 8-carbazole-6 }
One, preparation 4,4 '-bis-bromo-6,6 '-bis-iodo-2,1,3 diazosulfides
This step is with the step 1 of embodiment 1.
Two, preparation 6,6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide)
This step is with the step 2 of embodiment 3.
Three, 9-methyl isophthalic acid, 8-bis-((4,4,5,5-tetramethyl--1, the assorted oxygen pentaborane of 3,2-bis-) carbazole
This step is with the step 3 of embodiment 2.
Four, preparation poly-{ 6-dimethyl thiophene is coughed up also [3,2-e:4,5-e] two (diazosulfide) for 9-methyl isophthalic acid, 8-carbazole-6 }
Under nitrogen protection, add 9-methyl isophthalic acid, 8-bis-((4; 4,5,5-tetramethyl--1; the assorted oxygen pentaborane of 3,2-bis-) carbazole (83.6mg, 0.2mmol), 6; 6-dimethyl-4,8-dibromo thiophene is coughed up also [3,2-e:4; 5-e] two (diazosulfide) (145.2mg, 0.3mmol) and toluene solvant 40mL be to reaction flask, and vacuumize deoxygenation and be filled with nitrogen; then add (0.07mg, 0.0001mmol) Pd (PPh
3)
4, 0.2mL Na
2cO
3(2M, 0.4mmol), is heated to 50 ℃ of reactions 6 hours.After reaction, in the reaction flask of product, add deionized water and toluene to extract, get organic phase, by the method for underpressure distillation by polymkeric substance/toluene solution evaporate to dryness to about 5mL left and right, splashed in 400mL dehydrated alcohol and constantly stirred, there is solid precipitation to separate out, after suction filtration, oven dry, obtain pressed powder.Pressed powder is dissolved with chloroform again, cross chromatography column with neutral alumina, organic solvent, methyl alcohol sedimentation are removed in decompression.Suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's.Methyl alcohol sedimentation, suction filtration.Under vacuum pump, taking out spends the night obtains product.
Polymkeric substance after purifying is carried out to GPC test, number-average molecular weight Mn ≈ 538, n=1.
Embodiment 6
The multipolymer of preparing take the embodiment of the present invention is active coating, prepares organic solar cell device.Its structure as shown in Figure 2, comprises the substrate of glass 11 stacking gradually, anode 12, middle supplementary layer 13, active coating 14 and negative electrode 15.Wherein, anode 12 is ITO, is preferably the tin indium oxide that square resistance is 10-20 Ω/, and middle supplementary layer 13 adopts poly-(3,4-Ethylenedioxy Thiophene): polystyrolsulfon acid matrix material, be called for short PEDOT:PSS(CLEVIOS P VP Al 4083); Active coating 14 comprises electron donor material and electron acceptor material, and electron donor material is polymkeric substance prepared by the embodiment of the present invention, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM); Negative electrode 15 is aluminium, and this device architecture can briefly be described as glass/ITO/PEDOT:PSS/ active coating/Al.
The preparation method of above-mentioned organic solar batteries device is summarized as follows: using substrate of glass as bottom, choose ito glass (with anode ITO layer, can buy) when making, thickness is 1.1mm, after ultrasonic cleaning, with oxygen-Plasma processing; Then supplementary layer PEDOT:PSS in the middle of applying on ito glass, thickness is 120nm; The multipolymer of again being prepared by the 10mg embodiment of the present invention is dissolved in 0.4mL dimethylbenzene, is dissolved in 8mg PCBM the solution blending that 0.4mL chlorobenzene obtains, and is spun on PEDOT:PSS rete, and thickness is about 130nm, obtains active coating; At vacuum condition (2 × 10
-3pa) lower evaporation cathodic metal aluminium, thickness is 120nm, obtains organic solar batteries device.Preparation method and the structure of the organic solar batteries device that contains multipolymer of the present invention are not limited to the present embodiment, can device suitably be improved or be modified.
Prepared organic solar batteries device using the multipolymer (P1, P2 and P3) of embodiment 1,2 and 3 preparations as active layer material respectively, obtained device 1,2 and 3, all preparation process are all carried out in the glove box that nitrogen inert atmosphere is provided.
By the I-E characteristic of Keithley236 current/voltage source-measuring system and test component, obtain the performance data of device in table 1.
Table 1
As seen from the data in Table 1, the energy conversion efficiency of the organic solar batteries that the multipolymer making with the present invention is prepared as active coating is 0.99 ~ 1.36, show of the present inventionly to contain 1, 8-carbazole-thiophene is coughed up and the multipolymer of two (diazosulfides) can mate preferably with solar spectrum, and containing 1, 8-carbazole-thiophene cough up and the carrier mobility of the multipolymer of two (diazosulfides) higher, can improve ratio and charge collection efficiency that current carrier arrives electrode, thereby raising effciency of energy transfer, and by improvement or modification to device architecture, can obtain higher effciency of energy transfer.
Embodiment 7
To the preparation containing the organic electroluminescence device of polymkeric substance of the present invention, its structure as shown in Figure 3:
The copolymer p 1 of preparing take embodiment 1 is luminescent layer, is prepared with organic electroluminescence devices, and its structure as shown in Figure 3, comprises the glass substrate 21 stacking gradually, transparent anode 22, anode buffer layer 23, luminescent layer 24, cathode buffer layer 25 and negative electrode 26.Wherein, transparent anode 22 is preferably the tin indium oxide that square resistance is 10-20 Ω/ (ITO) (150nm), and anode buffer layer 23 adopts PEDOT:PSS(CLEVIOS P VPAl 4083) preparation (30nm); The copolymer p 1(100nm that luminescent layer 24 is prepared for embodiment 1), cathode buffer layer 25 is LiF (1.5nm), negative electrode 26 is metal A l (150nm), the structure of device is: glass/ITO/PEDOT:PSS/ copolymer p 1/LiF/Al, but the structure of practical devices is not limited to this.
Tested the electric current-brightness-voltage characteristic of above-mentioned organic electroluminescence device by Keithley source measuring system (Keithley 2400 Sourcemeter), with French its electroluminescent spectrum of the JY SPEX CCD3000 of company spectrometer measurement, all measurements all complete in atmosphere at room temperature, the high-high brightness efficiency that records organic electroluminescence device is 14.2cd/A, and high-high brightness is 1180cd/m
2.The above results shows, multipolymer prepared by embodiment 1 can improve luminance efficiency and high-high brightness as the luminescent layer of organic electroluminescence device.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (10)
1. cough up the also multipolymer of two (diazosulfides) containing 8-carbazole-thiophene, it is characterized in that thering is following structural formula:
Wherein, the integer that n is 1 ~ 100; R
1, R
2, R
3for C
1~ C
20alkyl.
2. cough up the also preparation method of the multipolymer of two (diazosulfides) containing 1,8-carbazole-thiophene for one kind, it is characterized in that, comprise the steps:
Compd A and compd B are provided, and the structural formula of compd A is:
Wherein, R
1, R
2for C
1~ C
20alkyl;
The structural formula of compd B is:
Wherein, R
3for C
1~ C
20alkyl;
Under the atmosphere of rare gas element, by compd A, compd B at catalyzer, solvent and Na
2cO
3under the condition existing, carry out Suzuki coupling reaction, wherein, the mol ratio of compd A and compd B is 1:1.5 ~ 1.5:1, temperature of reaction is 50 ° of C ~ 120 ° C, time is 6 ~ 100 hours, after separation and purification, obtain having coughing up and the multipolymer of two (diazosulfides) containing 1,8-carbazole-thiophene of following structural formula:
Wherein, the integer that n is 1 ~ 100.
3. 1, the 8-carbazole-thiophene that contains according to claim 2 is coughed up the also preparation method of the multipolymer of two (diazosulfides), it is characterized in that, described catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4or Pd (PPh
3)
2cl
2; The consumption of catalyzer be compd A molar weight 0.05% ~ 20%; Described solvent is tetrahydrofuran (THF), glycol dimethyl ether, ether, benzene or toluene;
The step of described separation and purification is:
In reaction system, add toluene and deionized water to extract, get organic phase, remove at least part of solvent of described organic phase by the method for underpressure distillation, again described organic phase is splashed into precipitating in anhydrous methanol, suction filtration, after oven dry, obtain pressed powder, again described pressed powder is dissolved with chloroform, remove catalyzer with neutral alumina chromatography column, finally remove chloroform, methyl alcohol sedimentation, suction filtration, gained solid extracts three days with acetone apparatus,Soxhlet's, methyl alcohol sedimentation, suction filtration, under vacuum pump, taking out spends the night after being purified containing 1, 8-carbazole-thiophene is coughed up the also multipolymer of two (diazosulfides).
4. 1, the 8-carbazole-thiophene that contains according to claim 2 is coughed up the also preparation method of the multipolymer of two (diazosulfides), it is characterized in that, described compd A is adopted preparation with the following method:
Compound C and Compound D are provided, and the structural formula of Compound C is:
The structural formula of Compound D is:
Under anhydrous and oxygen-free reaction conditions, Compound C is dissolved in to enough N, dinethylformamide, slowly drips n-Butyl Lithium, stirring reaction 2 hours, wherein the mol ratio of Compound C and n-Butyl Lithium is 1:2 ~ 1:4, then under-90 ° of C, slowly inject Compound D, react 10 hours after being warmed up to room temperature, after stopped reaction, washing, anhydrous diethyl ether extraction, gets organic phase, anhydrous sodium sulfate drying, filter, underpressure distillation, silica gel column chromatography separates, and obtains described compd A, wherein, the mol ratio of Compound D and Compound C is 1:2.
5. 1, the 8-carbazole-thiophene that contains according to claim 4 is coughed up the also preparation method of the multipolymer of two (diazosulfides), it is characterized in that, described Compound C is adopted preparation with the following method:
Compd E is provided, and the structural formula of compd E is:
Compd E is dissolved in tetrahydrofuran (THF), adds SnCl
2, be warming up to 100 ℃, reflux 10 hours, stopped reaction, cooling, with sodium hydroxide solution adjust pH to 8.0, anhydrous diethyl ether extraction, revolve and steam gained organic layer, obtain solid crude product, add hydrochloric acid, agitation and dropping sodium nitrite solution in 30 minutes, temperature is controlled at below 5 ℃, after dropwising, react 30 minutes, then reacted solution is added dropwise in liquor kalii iodide, vigorous stirring, react 12 hours, stopped reaction, with sodium hydroxide solution adjust pH to 7.0, extract with anhydrous diethyl ether, washing organic layer, use anhydrous magnesium sulfate drying, filter, revolve evaporate to dryness filtrate, separate with silica gel column chromatography, then carry out recrystallizing methanol, obtain Compound C.
6. 1, the 8-carbazole-thiophene that contains according to claim 5 is coughed up the also preparation method of the multipolymer of two (diazosulfides), it is characterized in that, described compd E is adopted preparation with the following method:
By bromo-4,7-bis-5-nitro-2,1,3 diazosulfide, copper powder, DMF mixes, be heated to 120 ℃ of reactions after 3 hours, be cooled to room temperature, add toluene, stir 30 minutes, filter, filtrate is used saturated aqueous common salt and water washing, merge organic layer, anhydrous magnesium sulfate drying, filters, revolve evaporate to dryness, dehydrated alcohol recrystallization, obtains compd E.
7. according to claim 6ly contain that 1,8-carbazole-thiophene is coughed up and the preparation method of the multipolymer of two (diazosulfides), it is characterized in that, described 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide is adopted preparation with the following method:
By 5-nitro-2,1,3 diazosulfide mixes with the Hydrogen bromide that mass concentration is 40%, be warming up to 127 ℃ of backflows, in 30 minutes, slowly drip bromine and reflux 4 hours, heat filtering, after filtrate is cooling, refilter, wash solid dry with water, with Glacial acetic acid recrystallization once, then with Gossypol recrystallized from chloroform once, obtain 4, the bromo-5-of 7-bis-nitro-2,1,3 diazosulfide.
8. 1, the 8-carbazole-thiophene that contains according to claim 7 is coughed up the also preparation method of the multipolymer of two (diazosulfides), it is characterized in that, and described 5-nitro-2,1,3 diazosulfide is adopted preparation with the following method:
2-amino-5-N-methyl-p-nitroaniline is mixed with thionyl chloride, stir and slowly drip pyridine, after heating in 80 ~ 90 ℃ of back flow reaction 24 hours, stopped reaction, is heated to 80 ℃ and revolves and steam after excessive thionyl chloride, and reaction product is cooled to room temperature, after stirring in the large water gaging of impouring, filtering, wash final vacuum is dried, obtain 5-nitro-2,1,3 diazosulfide.
9. 1, the 8-carbazole-thiophene that contains according to claim 2 is coughed up the also preparation method of the multipolymer of two (diazosulfides), it is characterized in that, described compd B is adopted preparation with the following method:
Compound F 17-hydroxy-corticosterone is provided, and the structural formula of compound F 17-hydroxy-corticosterone is:
Under atmosphere of inert gases, compound F 17-hydroxy-corticosterone is dissolved in to tetrahydrofuran (THF), at-78 ℃, slowly add n-Butyl Lithium, wherein, the mol ratio of compound F 17-hydroxy-corticosterone and n-Butyl Lithium is 1:2, stirring reaction 1 ~ 2 hour, then add 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, the assorted oxygen pentaborane of 2-bis-, 2-isopropoxy-4, 4, 5, 5-tetramethyl--1, 3, 2 times of the molar weight that the molar weight of the assorted oxygen pentaboranes of 2-bis-is compound F 17-hydroxy-corticosterone, continue at-78 ℃, to react 1 hour, then be warming up to room temperature, react 6 hours, add saturated sodium-chloride water solution termination reaction, extract with anhydrous diethyl ether, anhydrous sodium sulfate drying, after suction filtration by filtrate collection and revolve and evaporate solvent, finally carry out silica gel column chromatography separation, obtain described compd B.
10. as claimed in claim 1ly contain that 1,8-carbazole-thiophene is coughed up and the multipolymer of two (diazosulfides) application in polymer solar cell device, organic electroluminescence device, organic field effect tube, organic optical storage and organic laser.
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Application publication date: 20140604 |