CN102234365A - Anthracene and benzothiadiazole copolymer, and preparation method and application thereof - Google Patents
Anthracene and benzothiadiazole copolymer, and preparation method and application thereof Download PDFInfo
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- CN102234365A CN102234365A CN2010101637409A CN201010163740A CN102234365A CN 102234365 A CN102234365 A CN 102234365A CN 2010101637409 A CN2010101637409 A CN 2010101637409A CN 201010163740 A CN201010163740 A CN 201010163740A CN 102234365 A CN102234365 A CN 102234365A
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- DPMLBRILKDAWJL-UHFFFAOYSA-N CCC(C(Br)=C)=C Chemical compound CCC(C(Br)=C)=C DPMLBRILKDAWJL-UHFFFAOYSA-N 0.000 description 1
- 0 CCCCCCCCC(C)Cc1cc2c(B3OC(C)(C)C(C)(C)O3)c(ccc(CC(*)CCCCCCCC)c3)c3c(B3OC(C)(C)C(C)(C)O3)c2cc1 Chemical compound CCCCCCCCC(C)Cc1cc2c(B3OC(C)(C)C(C)(C)O3)c(ccc(CC(*)CCCCCCCC)c3)c3c(B3OC(C)(C)C(C)(C)O3)c2cc1 0.000 description 1
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Abstract
The invention discloses an anthracene and benzothiadiazole copolymer, and a preparation method and application thereof. The anthracene and benzothiadiazole copolymer has a general molecular structure formula shown in (I), wherein R1 and R2 are selected from -H, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted aryl, and substituted or unsubstituted heteroaryl, cyano or halogen; R3 and R4 are selected from -H, substituted or unsubstituted C1-C40 alkyl, substituted or unsubstituted C1-C40 alkoxy, substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C6-C40 arylalkyl, and substituted or unsubstituted C6-C40 alkoxy or cyano; n is the polymerization degree and is a natural number ranging from 1 to 500; and Ar is an organic group with an electron donating property. The anthracene and benzothiadiazole copolymer disclosed by the invention has the advantages of low energy gap, high carrier mobility and wide spectral absorption range, and improves the photoelectric conversion efficiency. The preparation method of the anthracene and benzothiadiazole copolymer is simple in process, high in product yield, and easy to operate and control.
Description
Technical field
The invention belongs to the organic compound synthesis technical field, relate to a kind of anthracene and diazosulfide analog copolymer and its production and application of containing specifically.
Background technology
High efficiency solar cell is a raw material with the inorganic semiconductor normally, and utilize cheap material preparation low cost, dynamical solar cell is the research focus and the difficult point in photovoltaic field always.Be used for the silicon solar cell on ground at present because the production process technology complexity is seriously polluted, power consumption is big, and the cost height has suppressed the development of its commercial applications.In order to reduce cost, expand range of application, people are seeking novel solar cell material always for a long time.Polymer solar battery receives much concern because of advantage such as mode large-area preparation such as cheap, the light weight of cost of material, flexibility, simple, the available coating of production technique, printing, if its energy conversion efficiency can be brought up to the level near the commodity silicon solar cell, its market outlook will be very huge.From report conjugated polymers and C on SCIENCE such as N.S.Sariciftci in 1992
60Between photoinduction transfer transport phenomenon after, people have dropped into big quantity research aspect polymer solar battery, and have obtained development at full speed.At present, the research of polymer solar battery mainly concentrates on to body, acceptor co-mixing system, adopt the energy conversion efficiency of PCPDTBT and PCBM co-mixing system to reach 6.5%, but it is still much lower than the efficiency of conversion of inorganic solar cell, the main restricting factor that limiting performance improves has: the carrier mobility that organic semiconductor device is relatively low, the spectral response of device and solar radiation spectrum do not match, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, a kind of anthracene and diazosulfide analog copolymer of containing is provided, this multipolymer energy gap is low, has increased carrier mobility, and its spectrographic absorption region is wide, and then has improved photoelectric transformation efficiency.
Another object of the present invention is to provide the preparation method who contains anthracene and diazosulfide analog copolymer that a kind of technology is simple, productive rate is high, be easy to operate and control.
Further aim of the present invention be to provide above-mentioned contain anthracene and diazosulfide analog copolymer at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and the organic laser Application for Field.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of anthracene and diazosulfide analog copolymer of containing, its general formula of molecular structure is following (I):
In the formula, R
1, R
2Be selected from-H, cyano group, halogen, or be selected from and replace or unsubstituted aryl, replacement or unsubstituted heteroaryl, replacement or unsubstituted C
1～C
40Alkyl; R
3, R
4Be selected from-H, cyano group, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted C
1～C
40Alkoxyl group, replacement or unsubstituted C
6～C
40Aryl, replacement or unsubstituted C
6～C
40Aralkyl, replacement or unsubstituted C
6～C
40Alkoxy aryl; N is the polymerization degree, and value is 1～500 natural number; Ar is the organic group that has to electronic property.
And a kind of anthracene and diazosulfide analog copolymer preparation method of containing comprises the steps:
The compd A, the B that provide following structural formula to represent respectively,
In anaerobic and alkaline environment and under the condition that catalyzer and organic solvent exist, compd A, B are carried out polyreaction, obtain following general structure and contain anthracene and diazosulfide analog copolymer for (I) expression, wherein, n is the polymerization degree, and value is 1～500 natural number
Further, provided by the invention contain anthracene and diazosulfide analog copolymer at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and the organic laser Application for Field.
The present invention compared with prior art possesses following advantage:
1. contain the diazosulfide unit that contains in anthracene and the diazosulfide analog copolymer molecule and have particular structure, this diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of metallic cathodes such as magnesium, aluminium, has electric transmission character preferably, can also regulate simultaneously the energy gap of material, thereby make this contain anthracene and the diazosulfide analog copolymer has lower energy gap, higher mobility, the spectrographic absorption region is wide, and makes this multipolymer more help current carrier to transmit effectively in active layer material inside.
2. the anthracene structural unit that contains has simultaneously effectively improved the stability and the film-forming properties of this multipolymer, the finger peak that makes this multipolymer uv-vis spectra present broad absorbs, effectively improve absorption coverage to sunlight, simultaneously, make this multipolymer it have suitable carrier transmission characteristics, hole mobility can reach 3cm under its crystal room temperature
2/ Vs;
3. this copolymer method is simple, the productive rate height, and the reaction conditions gentleness is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the synoptic diagram that contains anthracene and diazosulfide analog copolymer general formula of molecular structure of the embodiment of the invention;
Fig. 2 be adopt the embodiment of the invention 1 preparation contain anthracene and diazosulfide analog copolymer PA-BFB is the structural representation of the organic solar batteries device of active coating;
Fig. 3 be adopt the embodiment of the invention 1 preparation contain anthracene and diazosulfide analog copolymer PA-BFB is the structural representation of the organic electroluminescence device of luminescent layer;
Fig. 4 be adopt the embodiment of the invention 1 preparation contain anthracene and diazosulfide analog copolymer PA-BFB is the structural representation of the organic field effect tube device of organic semiconductor layer.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, what show the embodiment of the invention contains anthracene and diazosulfide analog copolymer, and its general formula of molecular structure is following (I):
In the formula, R
1, R
2Be selected from-H, cyano group, halogen, or be selected from and replace or unsubstituted aryl, replacement or unsubstituted heteroaryl, replacement or unsubstituted C
1～C
40Alkyl;
R
3, R
4Be selected from-H, cyano group, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted C
1～C
40Alkoxyl group, replacement or unsubstituted C
6～C
40Aryl, replacement or unsubstituted C
6～C
40Aralkyl, replacement or unsubstituted C
6～C
40Alkoxy aryl;
Above-mentioned R
1, R
2, R
3, R
4Can on corresponding phenyl ring, replace commutable optional position.
N is the polymerization degree, and value is 1～500 natural number;
Ar is the organic group that has to electronic property.
Above-mentioned C
1～C
40Alkyl is preferably straight chain, side chain or cyclic C
1～C
40Alkyl;
Described aryl, heteroaryl, aralkyl, alkoxy aryl, alkyl are or/and alkoxyl group is it single replacement or polysubstituted group.
Above-mentioned Ar is preferably one or more the group unit in the following general structural formula:
Wherein, a, b are 1,2 or 3, R
5～R
20Group for identical or different is preferably-H, cyano group, or is selected from and replaces or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted C
1～C
40Alkoxyl group, replacement or unsubstituted C
6～C
40Aryl, replacement or unsubstituted C
6～C
40Aralkyl, replacement or unsubstituted C
6～C
40Alkoxy aryl.Further, wherein said C
1～C
40Alkyl is preferably straight chain, side chain or cyclic C
1～C
40Alkyl; Described aryl, heteroaryl, aralkyl, alkoxy aryl, alkyl are or/and alkoxyl group is it single replacement or polysubstituted group.
The diazosulfide unit that contains in anthracene and the diazosulfide analog copolymer molecule that contains that the foregoing description provides has particular structure, this diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of metallic cathodes such as magnesium, aluminium, has electric transmission character preferably, can also regulate simultaneously the energy gap of material, thereby make this contain anthracene and the diazosulfide analog copolymer has lower energy gap, higher mobility, the spectrographic absorption region is wide, and makes this multipolymer more help current carrier to transmit effectively in active layer material inside.
The anthracene structural unit that this multipolymer contains has simultaneously effectively improved the stability and the film-forming properties of this multipolymer, the finger peak that makes this multipolymer uv-vis spectra present broad absorbs, effectively improve absorption coverage to sunlight, simultaneously, make this multipolymer it have suitable carrier transmission characteristics, hole mobility can reach 3cm under its crystal room temperature
2/ Vs.
Behind the process of the multipolymer among the present invention high temperature annealing, order and the regularity arranged between each group of intramolecularly and molecule segment have effectively been strengthened, the transmission speed and the efficient of carrier mobility have been improved, and then improved photoelectric transformation efficiency, thereby expanded this polymkeric substance at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and organic laser Application for Field scope.
And the embodiment of the invention also provides this to contain anthracene and diazosulfide analog copolymer preparation method, comprises following chemical equation:
The processing step that promptly specifically comprises is:
The compd A, the B that provide following structural formula to represent respectively,
Wherein, R
1, R
2Be selected from-H, cyano group, halogen, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted aryl, replacement or unsubstituted heteroaryl; R
3, R
4Be selected from-H, cyano group, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted C
1～C
40Alkoxyl group, replacement or unsubstituted C
6～C
40Aryl, replacement or unsubstituted C
6～C
40Aralkyl, replacement or unsubstituted C
6～C
40Alkoxy aryl, Ar are the organic group that has to electronic property;
In anaerobic and alkaline environment and under the condition of catalyzer and organic solvent existence, compd A, B are carried out polyreaction by the ratio of stoichiometric number, obtain following general structure and contain anthracene and diazosulfide analog copolymer for (I) expression, wherein, n is the polymerization degree, value is 1～500 natural number
The preparation of above-claimed cpd A and compd B can adopt present technique field preparation method commonly used to make, and as compd A, is example with embodiment 1, and it can adopt but be not limited to the preparation method of step 1 among the embodiment 1; Compd B is an example with embodiment 1, and it can adopt but be not limited to the preparation method of step 2 among the embodiment 1.Involved other the compound of present method all is the method preparations according to the present technique field.
The temperature of above-mentioned polyreaction is preferably 60～120 ℃, and the reaction times is 24～168 hours.The mol ratio of described compd A and compd B is 1: 1～1.5.Described catalyzer addition is preferably 0.5%～15% of described compd A molar percentage, it is preferably the mixture of organic palladium or organic palladium and organophosphorus ligand, when catalyzer is selected from the mixture of organic palladium and organophosphorus ligand, the mol ratio of organic palladium and organophosphorus ligand is preferably 1: 2～and 20, this organic palladium catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2In at least a.This polyreaction needs catalyzer, because this polyreaction needs participating in of catalyzer, produces intermediate product with a reactant wherein in described polymerization process, makes this Stille coupling reaction finally can realize.
The mol ratio of the addition of alkali and described compd A is preferably 3～10 in the alkaline environment of above-mentioned polyreaction: 1, this alkali is preferably at least a in alkali metal hydroxide, alkaline carbonate, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, triethylamine, the ammoniacal liquor, in order to accelerate this polymerization rate, preferably become the certain density aqueous solution to add to again in this polymerization reaction system the alkali configured in advance.Organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, N in this polyreaction, one or more in dinethylformamide, benzene or the toluene, and organic reaction solvent capacity, and minimum amount should guarantee that this polyreaction carries out smoothly.
Above-mentioned polyreaction also should be carried out in oxygen-free environment, this oxygen-free environment can adopt vacuum or be full of rare gas element and realize, preferably is full of rare gas element and realizes oxygen-free environment, and this rare gas element is a present technique field rare gas element commonly used, for example nitrogen, argon gas etc., preferred nitrogen.This is because the reactant and the oxygen of this polyreaction all is the quite active compositions of chemical property, when this polymer reaction system under the condition that aerobic exists, the preferential and combination with oxygen of reactant also reacts, thereby has stoped the forward of this polyreaction to carry out.Also can be further to polyreaction generate contain anthracene and the diazosulfide analog copolymer carries out The high temperature anneal, with order and the regularity of arranging between each group and molecule segment in the enhancing copolymer molecule, improve the transmission speed and the efficient of its carrier mobility, and then improve photoelectric transformation efficiency.
Contain among anthracene and the diazosulfide analog copolymer preparation method at this, only need that reactant is pressed ratio and add, need not special equipment and environmental requirement, its preparation method technology is simple, and productive rate height, and mild condition are easy to operate and control, and are suitable for suitability for industrialized production.
Because the present invention contains anthracene and the diazosulfide analog copolymer has above-mentioned advantage, therefore, this contains anthracene and the diazosulfide analog copolymer can be at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and use in the organic laser field.
Below illustrate the present invention by a plurality of embodiment and contain different structure of anthracene and diazosulfide analog copolymer and preparation method thereof, with and aspects such as application and performance.
Embodiment 1
Contain the preparation of anthracene and diazosulfide analog copolymer PA-BFB, its structural formula is as follows:
1) 9, the preparation of 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-anthracene, its reaction is shown below:
The preparation detailed process is: put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under; in there-necked flask, add 9 of light yellow crystal shape; 10-dibromoanthracene 9.0mmol; inject 150ml purified tetrahydrofuran solvent with syringe again; then slowly inject 27.0mmol n-BuLi with syringe under-78 ℃ of conditions and react, system is gradually by the faint yellow orange that becomes.Behind the stirring reaction 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes, system is become faint yellow by orange, be warmed up to room temperature reaction and spend the night.Reaction adds the saturated NaCl aqueous solution, chloroform extraction after finishing, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve to steam solvent and obtain crude product, then with the crude product sherwood oil: ethyl acetate (v/v=15: 1), obtain pulverulent solids for leacheate carries out the silica gel column chromatography separation.The GC-MS of this pulverulent solids (EI-m/z): 430 (M+).
2) 2,7-two (4-bromo-2,1,3-diazosulfide) base-9, the preparation of 9-dioctyl fluorene, its reaction is shown below:
The preparation detailed process is: add 4-bromo-2,1 in reactor, 3-diazosulfide 2mmol, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the Na of 9-dioctyl fluorene 1mmol, tetra-triphenylphosphine palladium 0.025mmol, 2mol/L
2CO
3Aqueous solution 5ml and toluene solvant 30ml are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, reaction is 80 hours under 100 ℃ of conditions, and reaction is after after processing later and the silicagel column purification, obtain pulverulent solids, productive rate 70%, this solid GC-MS (EI-m/z): 659 (M
+); With above-mentioned solid product at CCl
4Add bromine under the system for solution, back flow reaction is after 8 hours, carries out aftertreatment and silicagel column and purifies, and obtains product, and promptly 2,7-two (4-bromo-2,1,3-diazosulfide) base-9,9-dioctyl fluorene, productive rate 65%, the GC-MS of this productive rate (EI-m/z): 817 (M
+).
3) preparation of copolymer p A-BFB, its reaction is shown below:
The preparation detailed process is: add 9 in reactor, 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) basic anthracene 1mmol, 2,7-two (4-bromo-2,1, the 3-diazosulfide) base-9, the Na of 9-dioctyl fluorene 1mmol, tetra-triphenylphosphine palladium 0.025mmol, 2mol/L
2CO
3Aqueous solution 5ml and toluene solvant 30ml are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, behind reaction 72h under 120 ℃ of conditions, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml, after it is splashed in the 300ml anhydrous methanol constantly stir about 4h, there is solid precipitation to separate out gradually, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column, remove the catalyzer tetra-triphenylphosphine palladium, polymers soln is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P A-BFB is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.Polymer P A-BFB is carried out the GPC test, number-average molecular weight Mn ≈ 74500, the polymkeric substance monodispersity is 1.5.
Embodiment 2
Contain the preparation of anthracene and diazosulfide analog copolymer PODA-BFB, its structural formula is as follows:
1) 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2, the preparation of 6-two (2-octyl-decyl) anthracene, its reaction is shown below:
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under, in there-necked flask, add 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 5mmol, inject 150ml purified tetrahydrofuran solvent with syringe again, then under-78 ℃ of conditions, slowly inject 15mmol n-BuLi with syringe again, stirring reaction 2 hours; React after 2 hours, under-78 ℃ of conditions, inject 15mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.After reaction finishes, add saturated sodium-chloride water solution, chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and steam solvent.Be that leacheate carries out the silica gel column chromatography separation with crude product with suitable solvent at last, obtain pulverulent solids.This pulverulent solids GC-MS (EI-m/z): 935 (M+).
2) 2,7-two (4-bromo-2,1,3-diazosulfide) base-9, the preparation of 9-dioctyl fluorene is as the step 2 of embodiment 1);
3) preparation of copolymer p ODA-BFB, its reaction is shown below:
In two mouthfuls of formula reactors, add 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2,6-two (2-octyl-decyl) anthracene 1mmol, 2,7-two (4-bromo-2,1,3-diazosulfide) base-9,9-dioctyl fluorene 1mmol, Pd (PPh
3)
2Cl
20.015mmol, NaOH aqueous solution 4ml and the glycol dinitrate ether solvents 20ml of 2mol/L, by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, behind reaction 48h under 90 ℃ of conditions, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with the polymers soln evaporate to dryness to about 5ml, after it is splashed in the 400ml anhydrous methanol constantly stir about 5h, there is solid precipitation to separate out gradually, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column, remove the catalyzer tetra-triphenylphosphine palladium, at last polymers soln is spin-dried for, at last polymer collection is dried with neutral alumina.Polymer P ODA-BFB is carried out the GPC test, number-average molecular weight Mn ≈ 67600, the polymkeric substance monodispersity is 1.7.
Embodiment 3
Contain the preparation of anthracene and diazosulfide analog copolymer PODA-BTB, its structural formula is as follows:
1) 9,10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-2, the preparation of 6-two (2-octyl-decyl) anthracene, its preparation method is as step 1) among the embodiment 2;
2) 2, the preparation technology of the basic fluorenes of 7-two (4-bromo-2,1,3-diazosulfide) and processing parameter are as the step 2 of embodiment 1), but corresponding reactant changed;
3) preparation of copolymer p ODA-BTB, its reaction is shown below:
In two mouthfuls of reactors, add 9,10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) base-2,6-two (2-octyl-decyl) anthracene 1mmol, 2, the basic thiophene 1mmol of 5-two (4-bromo-2,1,3-diazosulfide), 1: 1 in molar ratio Pd
2(dba)
3With tetraethyl ammonium hydroxide aqueous solution 4ml and the glycol dimethyl ether 30ml of tetra-triphenylphosphine palladium mixed catalyst 0.015mmol, 2mol/L, by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, behind reaction 168h under 60 ℃ of conditions, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with the polymers soln evaporate to dryness to about 5ml, after it is splashed in the 400ml anhydrous methanol constantly stir about 4h, there is solid precipitation to separate out gradually, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column, remove the catalyzer tetra-triphenylphosphine palladium, at last polymers soln is spin-dried for, at last polymer collection is dried with neutral alumina.Polymer P ODA-BTB is carried out the GPC test, number-average molecular weight Mn ≈ 11000, the polymkeric substance monodispersity is 1.9.
Embodiment 4
Contain the preparation of anthracene and diazosulfide analog copolymer PA-BBB, its structural formula is as follows:
1) 9, the preparation of the basic anthracene of 10-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes), its preparation method is as step 1) among the embodiment 2;
2) to the preparation of the basic benzene of two (4-bromo-5, the two tetradecyloxyanilines-2,1 of 6-, 3-diazosulfides), its reaction is shown below:
Stoichiometric ratio by each reactant in the above-mentioned reaction formula is added corresponding reactant, the step 2 of its concrete reaction process and processing parameter and embodiment 1 is similar, subsequent purification is also identical, finally obtain product, promptly to two (4-bromo-5, the two tetradecyloxyanilines-2,1 of 6-, the 3-diazosulfide) basic benzene, the GC-MS of this product (EI-m/z): 1354 (M+).
3) preparation of copolymer p A-BBB, its reaction is shown below:
In reactor, add 9, the basic anthracene 1mmol of 10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two), to the basic benzene 1mmol of two (4-bromo-5, the two tetradecyloxyanilines-2,1 of 6-, 3-diazosulfides), 1: 10 in molar ratio Pd
2(dba)
3/ P (o-Tol)
3That mixed catalyst 0.025mmol, 2mol/L is 1: 2 Na in molar ratio
2CO
3With tetraethyl ammonium hydroxide water mixed liquid solution 5ml and glycol dinitrate ether solvents 30ml, make reaction system be in anaerobic state by leading to argon gas repeatedly and vacuumizing, behind reaction 70h under 90 ℃ of conditions, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml, after it is splashed in the 300ml anhydrous methanol constantly stir about 4h, there is solid precipitation to separate out gradually, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column, remove the catalyzer tetra-triphenylphosphine palladium, polymers soln is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P A-BBB is collected oven dry with neutral alumina.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.Polymer P A-BBB is carried out the GPC test, number-average molecular weight Mn ≈ 56000, the polymkeric substance monodispersity is 1.8.
Application Example 5
With the PA-BFB of embodiment 1 preparation preparation as the solar cell device of active coating:
See also Fig. 2, this solar cell device comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14, the negative electrode 15 that stacks gradually, middle supplementary layer 13 adopts polyethylene dioxy base thiophene: polystyrene-sulfonic acid matrix material (abbreviating PEDOT:PSS as), active coating 14 comprises electron donor material and electron acceptor material, electron donor material adopts PA-BFB, electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (abbreviating PCBM as).Transparent anode 12 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, for example Ca/Al or Ba/Al etc.Wherein, glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, handle with oxygen-Plasma, supplementary layer 13 in the middle of applying on ito glass on the supplementary layer 13, forms active coating 14 in the middle of PA-BFB and electron acceptor material being coated on after by blend again, and then, obtain above-mentioned solar cell device by vacuum evaporation technology deposition cathode 15 on active coating 14.In a preferred embodiment, the thickness of transparent anode 12, middle supplementary layer 13, active coating 14, double-metal layer Ca and Al layer be respectively 180,30,200,80nm.
As shown in Figure 2, under illumination, light transmission glass-base 11 and ITO electrode 12, the PA-BFB in the active coating 14 absorbs luminous energy, and produces exciton, these excitons are moved to electron donor(ED)/acceptor material at the interface again, and give electron acceptor material with transfer transport, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, freely the hole along electron donor material to ito anode transmission and collected by anode, thereby form photoelectric current and photovoltage, realize opto-electronic conversion, during external load 16, can power to it.In this process, PA-BFB can utilize luminous energy more fully because it has very wide spectral response range, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, is convenient to large batch of preparation.With this device with epoxy encapsulation after, place under 120 ℃ of air tight conditions annealing 3 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved the transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Application Example 6
Contain the preparation of the organic electroluminescence device of PA-BFB:
See also Fig. 3, show the organic electroluminescence device that adopts PA-BFB, it comprises glass-base 21, transparent anode 22, luminescent layer 23, buffer layer 24, the negative electrode 25 that is cascading.Transparent anode 22 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Luminescent layer 23 comprises PA-BFB.Buffer layer 24 can adopt LiF etc., but is not limited thereto.Negative electrode 25 can be but be not limited to metal A l etc.Thereby in a specific embodiment, the organic electroluminescence device structural table is shown: ITO/PA-BFB/LiF/Al.Each layer can adopt existing method to form, and PA-BFB can be formed on the ITO by spin coating technique.On this luminescent layer, can adopt vacuum evaporation LiF buffer layer, on buffer layer, can adopt evaporation metal Al, as the negative electrode of device.
Application Example 7
Contain the preparation of the organic field effect tube of PA-BFB:
See also Fig. 4, this organic field effect tube comprises substrate 31, insulation layer 32, decorative layer 33, the organic semiconductor layer 34 that is cascading and is located at source electrode 35 and drain electrode 36 on the organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si) that insulation layer 32 can be but be not limited to micro-nano (as 500nm) thick SiO
2 Organic semiconductor layer 34 adopts PA-BFB.Source electrode 35 and drain electrode 36 all can adopt but be not limited to gold.Decorative layer 33 can be but be not limited to octadecyl trichlorosilane (OTS).Substrate 31, insulation layer 32, decorative layer 33 and source electrode 35 and drain electrode 36 all can adopt existing method to form.Organic semiconductor layer 34 can be that PA-BFB is spun on the insulation layer of being modified by decorative layer 33 32.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind contains anthracene and diazosulfide analog copolymer, and its general formula of molecular structure is following (I):
In the formula, R
1, R
2Be selected from-H, cyano group, halogen, or be selected from and replace or unsubstituted aryl, replacement or unsubstituted heteroaryl, replacement or unsubstituted C
1～C
40Alkyl;
R
3, R
4Be selected from-H, cyano group, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted C
1～C
40Alkoxyl group, replacement or unsubstituted C
6～C
40Aryl, replacement or unsubstituted C
6～C
40Aralkyl, replacement or unsubstituted C
6～C
40Alkoxy aryl;
N is the polymerization degree, and value is 1～500 natural number;
Ar is the organic group that has to electronic property.
2. anthracene and the diazosulfide analog copolymer of containing according to claim 1 is characterized in that:
Described C
1～C
40Alkyl is straight chain, side chain or cyclic C
1～C
40Alkyl;
Described aryl, heteroaryl, aralkyl, alkoxy aryl, alkyl are or/and alkoxyl group is it single replacement or polysubstituted group.
3. anthracene and the diazosulfide analog copolymer of containing according to claim 1 is characterized in that:
Described Ar is one or more the group unit in the following general structural formula:
Wherein, a, b are 1,2 or 3, R
5～R
20Be selected from-H, cyano group, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted C
1～C
40Alkoxyl group, replacement or unsubstituted C
6～C
40Aryl, replacement or unsubstituted C
6～C
40Aralkyl, replacement or unsubstituted C
6～C
40Alkoxy aryl.
4. anthracene and the diazosulfide analog copolymer of containing according to claim 3 is characterized in that:
Described R
5～R
20C
1～C
40Alkyl is straight chain, side chain or cyclic C
1～C
40Alkyl;
Described aryl, heteroaryl, aralkyl, alkoxy aryl, alkyl are or/and alkoxyl group is it single replacement or polysubstituted group.
5. one kind contains anthracene and diazosulfide analog copolymer preparation method, comprises the steps:
The compd A, the B that provide following structural formula to represent respectively,
Wherein, R
1, R
2Be selected from-H, cyano group, halogen, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted aryl, replacement or unsubstituted heteroaryl; R
3, R
4Be selected from-H, cyano group, or be selected from and replace or unsubstituted C
1～C
40Alkyl, replacement or unsubstituted C
1～C
40Alkoxyl group, replacement or unsubstituted C
6～C
40Aryl, replacement or unsubstituted C
6～C
40Aralkyl, replacement or unsubstituted C
6～C
40Alkoxy aryl, Ar are the organic group that has to electronic property;
In anaerobic and alkaline environment and under the condition that catalyzer and organic solvent exist, compd A and compd B are carried out polyreaction, obtain following general structure and contain anthracene and diazosulfide analog copolymer for (I) expression, wherein, n is the polymerization degree, and value is 1～500 natural number
6. anthracene and the diazosulfide analog copolymer preparation method of containing according to claim 5, it is characterized in that: the catalyzer addition is 0.5%～15% of a described compd A mole dosage in the described polyreaction;
Described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand.
7. anthracene and the diazosulfide analog copolymer preparation method of containing according to claim 5, it is characterized in that: described organic palladium catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2In at least a.
8. anthracene and the diazosulfide analog copolymer preparation method of containing according to claim 5, it is characterized in that: the mol ratio of the addition of alkali and described compd A is 3～10: 1 in the alkaline environment of described polyreaction;
Described alkali is at least a in alkali metal hydroxide, alkaline carbonate, tetraethyl ammonium hydroxide, the ammoniacal liquor.
9. anthracene and the diazosulfide analog copolymer preparation method of containing according to claim 5, it is characterized in that: the mol ratio of compd A and compd B described in the described polyreaction is 1: 1～1.5
Described organic solvent is tetrahydrofuran (THF), glycol dimethyl ether, N, one or more in dinethylformamide, benzene or the toluene;
The temperature of reaction of described polyreaction is 60～120 ℃, and the reaction times is 24～168 hours.
According to claim 1 to 4 each described contain anthracene and diazosulfide analog copolymer at organic photoelectrical material, polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and the organic laser Application for Field.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833985A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | [3,2-b]bi-thiofuran-benzo-2(benzo-selenium diazole) combined copolymer as well as preparation method and application thereof |
| WO2015029910A1 (en) * | 2013-08-30 | 2015-03-05 | 富士フイルム株式会社 | Organic semiconductor device, as well as compound, composition, and coating film for same |
| KR20160031958A (en) * | 2014-09-15 | 2016-03-23 | 한국화학연구원 | Novel organic semiconductor compounds containing benzothiadiazole group, its manufacturing method and organic semiconductor device using the same |
| EP3121211A4 (en) * | 2014-03-21 | 2017-11-01 | LG Chem, Ltd. | Polymer and organic solar cell comprising same |
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| WO2010026972A1 (en) * | 2008-09-03 | 2010-03-11 | 住友化学株式会社 | Polymer compound and polymer light-emitting element utilizing same |
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| WO2010026972A1 (en) * | 2008-09-03 | 2010-03-11 | 住友化学株式会社 | Polymer compound and polymer light-emitting element utilizing same |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103833985A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | [3,2-b]bi-thiofuran-benzo-2(benzo-selenium diazole) combined copolymer as well as preparation method and application thereof |
| CN103833985B (en) * | 2012-11-27 | 2016-02-10 | 海洋王照明科技股份有限公司 | And [3,2-b] two thiophene-benzo two (selenole) multipolymer and its preparation method and application |
| WO2015029910A1 (en) * | 2013-08-30 | 2015-03-05 | 富士フイルム株式会社 | Organic semiconductor device, as well as compound, composition, and coating film for same |
| JP2015050231A (en) * | 2013-08-30 | 2015-03-16 | 富士フイルム株式会社 | Organic semiconductor device, compound to be used therefor, composition and coating film |
| EP3121211A4 (en) * | 2014-03-21 | 2017-11-01 | LG Chem, Ltd. | Polymer and organic solar cell comprising same |
| KR20160031958A (en) * | 2014-09-15 | 2016-03-23 | 한국화학연구원 | Novel organic semiconductor compounds containing benzothiadiazole group, its manufacturing method and organic semiconductor device using the same |
| KR101707028B1 (en) * | 2014-09-15 | 2017-02-16 | 한국화학연구원 | Novel organic semiconductor compounds containing benzothiadiazole group, its manufacturing method and organic semiconductor device using the same |
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