CN102234365B - 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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- CN102234365B CN102234365B CN 201010163740 CN201010163740A CN102234365B CN 102234365 B CN102234365 B CN 102234365B CN 201010163740 CN201010163740 CN 201010163740 CN 201010163740 A CN201010163740 A CN 201010163740A CN 102234365 B CN102234365 B CN 102234365B
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- 0 *C1(*)C2=C*S=C2C2=S*C=C12 Chemical compound *C1(*)C2=C*S=C2C2=S*C=C12 0.000 description 6
- IQTFTCHSXAYQQF-UHFFFAOYSA-N BC(C)c1cccc2n[s]nc12 Chemical compound BC(C)c1cccc2n[s]nc12 IQTFTCHSXAYQQF-UHFFFAOYSA-N 0.000 description 1
- DPMLBRILKDAWJL-UHFFFAOYSA-N CCC(C(Br)=C)=C Chemical compound CCC(C(Br)=C)=C DPMLBRILKDAWJL-UHFFFAOYSA-N 0.000 description 1
- LXNHJMWAMJEYJH-UHFFFAOYSA-N CCC(C=C12)SN=C1C([AlH]c(c1n[s]nc11)ccc1[BrH+])=CC=C2Br Chemical compound CCC(C=C12)SN=C1C([AlH]c(c1n[s]nc11)ccc1[BrH+])=CC=C2Br LXNHJMWAMJEYJH-UHFFFAOYSA-N 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 specifically a kind of anthracene and diazosulfide copolymer and its preparation method and application of containing.
Background technology
High efficiency solar cell is normally take inorganic semiconductor as raw material, and utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Be used at present the silicon solar cell on ground because production process technology is complicated, seriously polluted, power consumption is large, and cost is high, has suppressed the development of its commercial applications.In order to reduce costs, expand range of application, people are seeking novel solar cell material always for a long time.Polymer solar battery receives much concern because of the advantage such as mode big area preparations such as cheap, the quality of cost of material is light, 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 the C on SCIENCE such as N.S.Sariciftci in 1992
60Between the 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 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 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 mate, 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 object of the invention is to overcome the above-mentioned deficiency of prior art, a kind of anthracene and diazosulfide copolymer of containing is provided, this multipolymer energy gap is low, has increased carrier mobility, and the absorption region of its spectrum 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 copolymer that a kind of technique is simple, productive rate is high, be easy to operate and control.
Further aim of the present invention is to provide above-mentioned and contains anthracene and diazosulfide 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 application in the organic laser field.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind of anthracene and diazosulfide copolymer of containing, its general formula of molecular structure are following (I):
In 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 copolymer preparation method of containing comprises the steps:
The compd A, the B that provide respectively following structural formula to represent,
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, B are carried out polyreaction, obtain following general structure and contain anthracene and diazosulfide copolymer for (I) expression, wherein, n is the polymerization degree, and value is 1～500 natural number
Further, provided by the inventionly contain anthracene and diazosulfide 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 application in the organic laser field.
The present invention compared with prior art possesses following advantage:
1. contain the diazosulfide unit that contains in anthracene and diazosulfide copolymer molecule and have unique structure, this diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the 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 diazosulfide copolymer has lower energy gap, higher mobility, the absorption region of spectrum is wide, and makes this multipolymer more be conducive to current carrier effectively to transmit in active layer material inside.
2. the anthracene structural unit that contains has simultaneously effectively improved stability and the film-forming properties of this multipolymer, make this multipolymer uv-vis spectra present wider finger peak absorption, effectively improve sun Optical Absorption coverage, simultaneously, it has suitable carrier transmission characteristics to make this multipolymer, and under its crystal room temperature, hole mobility can reach 3cm
2/ Vs;
3. this multipolymer preparation method is simple, and productive rate is high, and reaction conditions is gentle, is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the schematic diagram that contains anthracene and diazosulfide copolymer general formula of molecular structure of the embodiment of the present invention;
Fig. 2 be adopt the embodiment of the present invention 1 preparation contain anthracene and diazosulfide copolymer PA-BFB is the structural representation of the organic solar batteries device of active coating;
Fig. 3 be adopt the embodiment of the present invention 1 preparation contain anthracene and diazosulfide copolymer PA-BFB is the structural representation of the organic electroluminescence device of luminescent layer;
Fig. 4 be adopt the embodiment of the present invention 1 preparation contain anthracene and diazosulfide 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, below in conjunction with embodiment, the present invention is further elaborated.Should be appreciated that specific embodiment described herein only in order to explain the present invention, is not intended to limit the present invention.
See also Fig. 1, what show the embodiment of the present invention contains anthracene and diazosulfide copolymer, and its general formula of molecular structure is following (I):
In 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 replace commutable optional position on corresponding phenyl ring.
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 the C of straight chain, side chain or ring-type
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 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 the C of straight chain, side chain or ring-type
1～C
40Alkyl; Described aryl, heteroaryl, aralkyl, alkoxy aryl, alkyl are or/and alkoxyl group is it single replacement or polysubstituted group.
Above-described embodiment provides contains the diazosulfide unit that contains in anthracene and diazosulfide copolymer molecule and has unique structure, this diazosulfide unit has excellent reduction reversibility, very approaching with the work content value of the 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 diazosulfide copolymer has lower energy gap, higher mobility, the absorption region of spectrum is wide, and makes this multipolymer more be conducive to current carrier effectively to transmit in active layer material inside.
The anthracene structural unit that this multipolymer contains has simultaneously effectively improved stability and the film-forming properties of this multipolymer, make this multipolymer uv-vis spectra present wider finger peak absorption, effectively improve sun Optical Absorption coverage, simultaneously, it has suitable carrier transmission characteristics to make this multipolymer, and under its crystal room temperature, hole mobility can reach 3cm
2/ Vs.
After the process of the multipolymer in the present invention high temperature annealing, order and the regularity arranged between interior each group of molecule and molecule segment have effectively been strengthened, 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 the range of application in the organic laser field.
And the embodiment of the present invention also provides this to contain anthracene and diazosulfide copolymer preparation method, comprises following chemical equation:
The processing step that namely specifically comprises is:
The compd A, the B that provide respectively following structural formula to represent,
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 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 the art preparation method commonly used to make, and as compd A, take embodiment 1 as example, it can adopt but be not limited to the preparation method of step 1 in embodiment 1; Compd B is take embodiment 1 as example, and it can adopt but be not limited to the preparation method of step 2 in embodiment 1.Involved other the compound of present method is all the method preparations according to the art.
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 catalyst loading 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.
In the alkaline environment of above-mentioned polyreaction, the mol ratio of the addition of alkali and described compd A is preferably 3～10: 1, this alkali is preferably at least a in alkali metal hydroxide, alkaline carbonate, tetraethyl ammonium hydroxide, Tetramethylammonium hydroxide, triethylamine, 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.In this polyreaction, organic solvent is one or more in tetrahydrofuran (THF), glycol dimethyl ether, DMF, benzene or 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 the art rare gas element commonly used, such as nitrogen, argon gas etc., preferred nitrogen.This is because reactant and the oxygen of this polyreaction is all the quite active compositions of chemical property, and 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 when this polymer reaction system.Also can be further to polyreaction generate contain anthracene and diazosulfide 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 transmission speed and the efficient of its carrier mobility, and then improve photoelectric transformation efficiency.
Contain in anthracene and diazosulfide copolymer preparation method at this, only need that reactant is pressed ratio and add, need not special equipment and environmental requirement, its preparation method technique is simple, and productive rate is high, and mild condition, is easy to operate and control, and is suitable for suitability for industrialized production.
Because the present invention contains anthracene and diazosulfide copolymer has advantages of above-mentioned, therefore, this contain anthracene and diazosulfide 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 copolymer and preparation method thereof, with and the aspects such as application and performance.
Embodiment 1
Contain the preparation of anthracene and diazosulfide copolymer PA-BFB, its structural formula is as follows:
1) 9, the preparation of 10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) 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; add 9 of light yellow crystal shape in there-necked flask; 10-dibromoanthracene 9.0mmol; inject the refining tetrahydrofuran solvent of 150ml with syringe again; then slowly inject 27.0mmol n-BuLi and react with syringe under-78 ℃ of conditions, system is gradually by the faint yellow orange that becomes.After stirring reaction 2 hours, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe under-78 ℃ of conditions, 5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two, system is become faint yellow by orange, be warmed up to room temperature reaction and spend the night.After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, after filtering with filtrate collection and revolve and evaporate solvent and obtain crude product, then with the crude product sherwood oil: ethyl acetate (v/v=15: 1) separate for leacheate carries out silica gel column chromatography, obtain pulverulent solids.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, the assorted oxygen pentaborane of 2-two) 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 repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, reaction is 80 hours under 100 ℃ of conditions, and reaction obtains pulverulent solids, productive rate 70%, this solid GC-MS (EI-m/z): 659 (M by after processing and silicagel column are purified later
+); With above-mentioned solid product at CCl
4Add bromine under system for solution, back flow reaction was carried out aftertreatment and silicagel column and is purified after 8 hours, obtained product, namely 2,7-two (4-bromo-2,1,3-diazosulfide) base-9, the 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 9,10-two (4,4,5 in reactor, 5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) basic anthracene 1mmol, 2,7-two (4-bromo-2,1,3-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 repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, after reaction 72h under 120 ℃ of conditions, add deionized water and toluene to extract in the reaction flask of product, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, after it is splashed in the 300ml anhydrous methanol constantly stir about 4h, there is gradually solid precipitation to separate out, through obtaining pressed powder after suction filtration, oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, polymers soln is revolved steam to surplus 5ml left and right at last, splash into it in methanol solvate and stirred for several hour, at last polymer P A-BFB is collected oven dry.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 copolymer PODA-BFB, its structural formula is as follows:
1) 9,10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) 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, add 9,10-, two bromo-2 in there-necked flask, 6-two (2-octyl-decyl) anthracene 5mmol, inject the refining tetrahydrofuran solvent of 150ml with syringe again, then slowly inject 15mmol n-BuLi with syringe again under-78 ℃ of conditions, stirring reaction 2 hours; React after 2 hours, inject 15mmol 2-isopropoxy-4,4,5 with syringe under-78 ℃ of conditions, 5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two is warmed up to room temperature reaction and spends 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 evaporate 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:
Add 9,10-two (4,4,5 in two mouthfuls of formula reactors, 5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) 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 repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, after reaction 48h under 90 ℃ of conditions, add deionized water and toluene to extract in the reaction flask of product, get organic phase, with the method for underpressure distillation with the polymers soln evaporate to dryness to about 5ml left and right, after it is splashed in the 400ml anhydrous methanol constantly stir about 5h, there is gradually solid precipitation to separate out, through obtaining pressed powder after suction filtration, oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymers soln is spin-dried for, at last polymer collection is dried.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 copolymer PODA-BTB, its structural formula is as follows:
1) 9,10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) base-2, the preparation of 6-two (2-octyl-decyl) anthracene, its preparation method is as step 1 in 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:
Add 9,10-two (4,4,5 in two mouthfuls of reactors, 5-tetramethyl--1,3, the assorted oxygen pentaborane 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), the Pd of 1: 1 in molar ratio
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 repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, after reaction 168h under 60 ℃ of conditions, add deionized water and toluene to extract in the reaction flask of product, get organic phase, with the method for underpressure distillation with the polymers soln evaporate to dryness to about 5ml left and right, after it is splashed in the 400ml anhydrous methanol constantly stir about 4h, there is gradually solid precipitation to separate out, through obtaining pressed powder after suction filtration, oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymers soln is spin-dried for, at last polymer collection is dried.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 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, the assorted oxygen pentaborane of 2-two), its preparation method is as step 1 in embodiment 2);
2) to the preparation of two (4-bromo-5, the two tetradecyloxyanilines-2,1 of 6-, 3-diazosulfide) basic benzene, its reaction is shown below:
Stoichiometric ratio by each reactant in above-mentioned reaction formula is added corresponding reactant, the step 2 of its concrete reaction process and processing parameter and embodiment 1 is similar, follow-up purification process is also identical, finally obtain product, namely 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:
Add the basic anthracene 1mmol of 9,10-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaborane of 2-two) in reactor, to two (4-bromo-5, the two tetradecyloxyanilines-2,1 of 6-, 3-diazosulfide) basic benzene 1mmol, the Pd of 1: 10 in molar ratio
2(dba)
3/ P (o-Tol)
3That mixed catalyst 0.025mmol, 2mol/L is the Na of 1: 2 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 repeatedly leading to argon gas and vacuumizing, after reaction 70h under 90 ℃ of conditions, add deionized water and toluene to extract in the reaction flask of product, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml left and right, after it is splashed in the 300ml anhydrous methanol constantly stir about 4h, there is gradually solid precipitation to separate out, through obtaining pressed powder after suction filtration, oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, polymers soln is revolved steam to surplus 5ml left and right at last, splash into it in methanol solvate and stirred for several hour, at last polymer P A-BBB is collected oven dry.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 the 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 (referred to as PEDOT:PSS), 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 (referred to as PCBM).Transparent anode 12 can adopt tin indium oxide (referred to as ITO), 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, such as Ca/Al or Ba/Al etc.Wherein, glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, process with oxygen-Plasma, supplementary layer 13 in the middle of applying on ito glass, then in the middle of PA-BFB and electron acceptor material are coated on after by blend on supplementary layer 13, form active coating 14, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device.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 active coating 14 absorbs luminous energy, and produces exciton, these excitons move to electron donor(ED)/acceptor material at the interface again, and with transfer transport to electron acceptor material, 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, the hole is along electron donor material to ito anode transmission and collected by anode freely, thereby forms photoelectric current and photovoltage, realizes 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, be placed under 120 ℃ of air tight conditions annealing 3 hours, then drop to room temperature.Due to device annealed after, the chemical structure of material is more regular in order, has improved 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 (referred to as ITO), 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 to this.Negative electrode 25 can be but be not limited to metal A l etc.Thereby in a specific embodiment, the organic electroluminescence device representation is: ITO/PA-BFB/LiF/Al.Each layer can adopt existing method to form, and PA-BFB can be formed on ITO by spin coating technique.Can adopt vacuum evaporation LiF buffer layer on this luminescent layer, can adopt evaporation metal Al on buffer layer, 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 organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si), and 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 alkane (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 32 of being modified by decorative layer 33.
The above is only preferred embodiment of the present invention, not in order to limiting the present invention, all any modifications of doing within the spirit and principles in the present invention, is equal to and replaces and improvement etc., within all should being included in protection scope of the present invention.
Claims (8)
1. one kind contains anthracene and diazosulfide copolymer, and its general formula of molecular structure is following (I):
In 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 the natural number greater than 1 to 500; Ar is one or more the group unit in following general structural formula:
Wherein, b is 1,2 or 3, R
6～R
11, R
19, 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.
2. anthracene and the diazosulfide copolymer of containing according to claim 1 is characterized in that:
Described C
1～C
40Alkyl is the C of straight chain, side chain or ring-type
1～C
40Alkyl;
Described aryl, heteroaryl, aralkyl, alkoxy aryl, alkyl are or/and alkoxyl group is it single replacement or polysubstituted group.
3. one kind contains anthracene and diazosulfide copolymer preparation method, comprises the steps:
The compd A, the B that provide respectively following structural formula to represent,
A：
B：
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 one or more the group unit in following general structural formula:
Wherein, b is 1,2 or 3, R
6～R
11, R
19, 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;
In anaerobic and alkaline environment and under the condition of catalyzer and organic solvent existence, compd A and compd B are carried out polyreaction, obtain following general structure and contain anthracene and diazosulfide copolymer for (I) expression, wherein, n is the polymerization degree, value is the natural number greater than 1 to 500
4. anthracene and the diazosulfide copolymer preparation method of containing according to claim 3, it is characterized in that: in described polyreaction, catalyst loading is 0.5%～15% of described compd A mole dosage;
Described catalyzer is the mixture of organic palladium or organic palladium and organophosphorus ligand.
5. anthracene and the diazosulfide copolymer preparation method of containing according to claim 3, 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.
6. anthracene and the diazosulfide copolymer preparation method of containing according to claim 3, it is characterized in that: in the alkaline environment of described polyreaction, the mol ratio of the addition of alkali and described compd A is 3～10: 1;
Described alkali is at least a in alkali metal hydroxide, alkaline carbonate, tetraethyl ammonium hydroxide, ammoniacal liquor.
7. anthracene and the diazosulfide copolymer preparation method of containing according to claim 3, it is characterized in that: the mol ratio of compd A and compd B described in described polyreaction is 1: 1～1.5
Described organic solvent is one or more in tetrahydrofuran (THF), glycol dimethyl ether, DMF, benzene or toluene;
The temperature of reaction of described polyreaction is 60～120 ℃, and the reaction times is 24～168 hours.
8. any one describedly contains anthracene and diazosulfide copolymer at polymer solar battery, organic electroluminescent, organic field effect tube, organic optical storage, organic non-linear optical properties or/and the application in the organic laser field according to claim 1 to 2.
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