CN104211921A - Conjugated polymer, preparation method and applications thereof - Google Patents

Conjugated polymer, preparation method and applications thereof Download PDF

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Publication number
CN104211921A
CN104211921A CN201310207006.1A CN201310207006A CN104211921A CN 104211921 A CN104211921 A CN 104211921A CN 201310207006 A CN201310207006 A CN 201310207006A CN 104211921 A CN104211921 A CN 104211921A
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reaction
organic
conjugated polymers
preparation
compd
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周明杰
管榕
李满园
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells

Abstract

The invention relates to a conjugated polymer represented by the formula (P), wherein in the formula the R represents an H atom or an alkyl group with a carbon number of 1 to 12, and the n represents a natural number between 5 and 60. The invention also relates to a preparation method and applications of the conjugated polymer. Compared to the prior art, the dithienylbenzoselenadiazole unit in the conjugated polymer is derived from benzodithienyl-4,5-dione and is also an excellent electron acceptor unit as benzo[2,1,3]selenadiazole. The thieno[3,2-b]thiophene is taken as the donor unit and is subjected to copolymerization reactions with two acceptor units namely dithienoselenadiazole derivatives and benzo[2,1,3]thiadiazole to form a D-A-D-A repeating unit. Through the electron pushing-pulling interactive effect between acceptors, the energy gap of the conjugated polymer is narrowed down, and thus the light absorption range of the conjugated polymer is largely increased.

Description

Conjugated polymers and preparation method thereof and application
Technical field
The present invention relates to field of light emitting materials, particularly relate to a kind of conjugated polymers.The invention still further relates to preparation method and the application of this conjugated polymers.
Background technology
Organic solar batteries is owing to having some incomparable advantages of inorganic solar cell, as with low cost, manufacture craft is simple, and product weight is light, the advantage such as can to prepare by large area flexible, make it get more and more people's extensive concerning as the potential renewable energy source of a kind of tool.In in the past 10 years, the performance of organic solar batteries has had and has steadily improved, and effciency of energy transfer is close to 10%.Although the effciency of energy transfer of organic solar batteries is greatly improved, up to the present, the photoelectric transformation efficiency of organic solar batteries is than inorganic solar cell or much lower.Therefore, want the commercialization realizing organic solar batteries, the organic semiconductor material of development of new is significant for the efficiency improving organic solar batteries.
Due to the progress in recent years in the design and device fabrication of conjugated polymers, the efficiency of polymer solar battery obtains large increase.One of following facing challenges of polymer solar battery is exactly the P-type conjugated polymers of synthesizing new, and it needs to possess following characteristics: (a) good solubility, is conducive to solvent processing, realizes suitability for industrialized production; B () has wide and strong absorption to whole sunlight spectrum; C carrier mobility that () is high, is conducive to carrier transport.Wherein how to widen the light abstraction width of polymer materials, making its light abstraction width farthest cover whole sunlight spectrum will be the emphasis studied.In semi-conducting polymer skeleton, select suitable monomer, be conducive to the light abstraction width of polymkeric substance to widen infrared, near-infrared region.One of strategy be wherein introduce in polymer backbone the donor monomer of electron rich and electron deficiency by body unit.By giving the interaction of this " pushing away-La electronics " in acceptor, reducing the energy gap of conjugated polymers, its absorption band is moved to infrared and near infrared low energy wave band.
Thieno-[3,2-b] thiophene, compared with thiophene, has higher carrier mobility.This is that thieno-[3,2-b] thiophene has expanded the coplanarity of polymkeric substance, makes whole molecular skeleton have the HOMO of delocalization more, thus improves the jump of intermolecular electric charge carrier.Thieno-[3,2-b] thiophene, as donor monomer, is extensively studied in organic polymer solar cell simultaneously.
Summary of the invention
The object of the invention is to solve above-mentioned prior art Problems existing and deficiency, a kind of conjugated polymers is provided, and the preparation method of this conjugated polymers and application.
The present invention is directed to above-mentioned technical problem and the technical scheme proposed is:
One has the conjugated polymers of following general formula (P):
Wherein, R is H or C 1~ C 12alkyl, n is the natural number between 5 ~ 60.
A preparation method for conjugated polymers, the method comprises the following steps:
A) following compd A and B is provided;
Compd A is
Compd B is
B) under atmosphere of inert gases, described compd A and described compd B are joined in organic solvent with mol ratio 1.1 ~ 1.5:1, catalyzer is added after dissolving, Stille coupling reaction is carried out 24 ~ 72 hours again at 60 ~ 120 DEG C, separating-purifying, obtains conjugated polymers (P);
Wherein, R is H or C 1~ C 12alkyl, n is the natural number between 5 ~ 60.
Reaction formula is as follows:
Described catalyzer can be tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; Or
Described catalyzer can also be the mixture of organic palladium and organophosphorus ligand, the mol ratio of described organic palladium and organophosphorus ligand is 1:2 ~ 20, described organic palladium is three (dibenzalacetone) two palladium, and described organophosphorus ligand is three (o-methyl-phenyl-) phosphine.
The mol ratio of described catalyzer and described compd A is 0.0001 ~ 0.05:1.
Rare gas element in described atmosphere of inert gases is one or both in nitrogen, argon gas.
Described organic solvent is the one in tetrahydrofuran (THF), DMF or toluene.
Described separating-purifying step is as follows: the reaction solution obtained by described Stille coupling reaction is by removing excessive solvent under reduced pressure, be added drop-wise to again in methyl alcohol and carry out sedimentation, by methanol wash after suction filtration, successively by the column chromatography of aluminum oxide and the drip washing of chloroform after drying, steam removing organic solvent again, suction filtration after methyl alcohol sedimentation, carries out surname extraction by the solid acetone of gained, suction filtration after methyl alcohol sedimentation, obtains described conjugated polymers again.
Compd A adopts following steps to obtain:
1), under atmosphere of inert gases, in reaction flask, add structural formula is successively alkylating 5,8-dibromo two thieno-s [3 ', 2 ': 3,4 of N-; 2 ' ', 3 ' ': 5,6] benzo [1,2-d] [1,2,5] selenium diazole (c), structural formula is the boric acid derivatives (d) of thieno-[3,2-b] thiophene, carbonate, palladium catalyst, reaction solvent, reactant, after 60 ~ 120 DEG C of stirring and refluxing reaction 24 ~ 72h, is cooled to room temperature, reaction solution is poured in distilled water, carry out cancellation reaction, then use dichloromethane extraction, wash with saturated common salt after merging organic phase, dry filter, silicagel column separation and purification obtains structural formula and is
verbindung; Wherein, 5,8-dibromo two thieno-[3 ', 2 ': 3,4; 2 ' ', 3 ' ': 5,6] mol ratio of the boric acid derivatives of benzo [1,2-d] [1,2,5] selenium diazole and thieno-[3,2-b] thiophene is 1:1.1 ~ 1:1.2; Carbonate makes alkali, and consumption is 5,8-dibromo two thieno-[3 ', 2 ': 3,4; 2 ' ', 3 ~ 5 times of 3 ' ': 5,6] benzo [1,2-d] [1,2,5] selenium diazole consumption; Palladium catalyst is Pd (PPh 3) 2cl 2or Pd (PPh 3) 4, consumption is 0.01% ~ 5% times of c mole dosage, and described solvent is the one in tetrahydrofuran (THF), DMF (DMF), dimethyl sulfoxide (DMSO);
2) under anhydrous and oxygen-free condition, described Verbindung is added in dry tetrahydrofuran (THF), and is cooled to-78 DEG C, slowly add the hexane solution of 2.5mol/L n-Butyl Lithium with syringe, finish, at-78 DEG C after stirring reaction 2 ~ 3h, then add the tetrahydrofuran solution of a certain amount of trimethyltin chloride, after insulation reaction 0.5 ~ 1h, return to room temperature, continue reaction 20 ~ 24h, stopped reaction, removes excessive solvent and trimethyltin chloride under reduced pressure, obtains described compd A; Wherein, n-Butyl Lithium and chlorination trimethyltin chloride are 2.2 ~ 2.5 times of described Verbindung consumption.
The invention still further relates to the application of above-mentioned conjugated polymers in organic electroluminescence device, organic field effect tube, organic solar batteries device, organic light storage device, organic non-linear optical properties or organic laser.
Compared with prior art, two thieno-s [3 ', 2 ': 3,4 in conjugated polymers of the present invention; 2 ' ', 3 ' ': 5,6] benzo [1,2-d] [1,2,5] oxadiazoles are at benzo [1,2-b:6,5-b '] two thiophene-4, the basis of 5-diketone derives, and it and benzo [2,1,3] selenium diazole are equally a kind of excellent electron acceptor(EA) unit.By thieno-[3,2-b] thiophene as donor monomer, be subject to body unit two thieno-[3 ', 2 ': 3,4 with two respectively; 2 ' ', 3 ' ': 5,6] [1,2,5] oxadiazole derivatives and benzo [2,1,3] selenium diazole copolymerization form the repeating unit of D-A-D-A to benzo [1,2-c].By giving the interaction of this " pushing away-La electronics " between acceptor, reducing the energy gap of conjugated polymers, substantially increasing the light abstraction width of material.
Accompanying drawing explanation
Fig. 1 is the structure iron of the organic solar batteries device applying conjugated polymers of the present invention.
Fig. 2 is the structure iron of the organic electroluminescence device applying conjugated polymers of the present invention.
Fig. 3 is the structure iron of the organic field effect tube device applying conjugated polymers of the present invention.
Embodiment
Below in conjunction with embodiment, elaboration is further given to the present invention.
Conjugated polymers of the present invention has following general formula (P):
One has the conjugated polymers of following general formula (P):
Wherein, R is H or C 1~ C 12alkyl, n is the natural number between 5 ~ 60.
The preparation method of above-mentioned conjugated polymers, comprises the following steps:
A) following compd A and B is provided;
Compd A is
Compd B is
B) under atmosphere of inert gases, described compd A and described compd B are joined in organic solvent with mol ratio 1.1 ~ 1.5:1, catalyzer is added after dissolving, Stille coupling reaction is carried out 24 ~ 72 hours again at 60 ~ 120 DEG C, separating-purifying, obtains conjugated polymers (P);
Wherein, R is H or C 1~ C 12alkyl, n is the natural number between 5 ~ 60.
Described catalyzer can be tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; Or
Described catalyzer can also be the mixture of organic palladium and organophosphorus ligand, the mol ratio of described organic palladium and organophosphorus ligand is 1:2 ~ 20, described organic palladium is three (dibenzalacetone) two palladium, and described organophosphorus ligand is three (o-methyl-phenyl-) phosphine.
The mol ratio of described catalyzer and described compd A is 0.0001 ~ 0.05:1.
Rare gas element in described atmosphere of inert gases is one or both in nitrogen, argon gas.Described organic solvent is the one in tetrahydrofuran (THF), DMF or toluene.
Above-mentioned steps b) in the concrete steps of purification by liquid extraction as follows: the reaction solution obtained by Stille coupling reaction is by removing excessive solvent under reduced pressure, be added drop-wise to again in methyl alcohol and carry out sedimentation, by methanol wash after suction filtration, successively by the column chromatography of aluminum oxide and the drip washing of chloroform after drying, steam removing organic solvent again, suction filtration after methyl alcohol sedimentation, carries out surname extraction by the solid acetone of gained, suction filtration after methyl alcohol sedimentation, obtains described conjugated polymers again.
In addition, the preparation scheme of compd A, comprises the steps:
1) under atmosphere of inert gases (rare gas element comprises nitrogen and argon gas etc.), in reaction flask, adding structural formula is successively alkylating 5,8-dibromo two thieno-s [3 ', 2 ': 3,4 of N-; 2 ' ', 3 ' ': 5,6] benzo [1,2-d] [1,2,5] selenium diazole (c), structural formula is the boric acid derivatives (d) of thieno-[3,2-b] thiophene, carbonate, palladium catalyst, reaction solvent.Reactant, after 60 ~ 120 DEG C of stirring and refluxing reaction 24 ~ 72h, is cooled to room temperature, is poured into by reaction solution in distilled water, carry out cancellation reaction.Use dichloromethane extraction again, wash with saturated common salt after merging organic phase, dry filter, silicagel column separation and purification obtains structural formula and is compound (e).Wherein said compound (c) is 1:1.1 ~ 1:1.2 with the mol ratio of compound (d); Carbonate makes alkali, generally adopts sodium carbonate, cesium carbonate, salt of wormwood, and consumption is 3 ~ 5 times of compound (c) consumption; Palladium catalyst is Pd (PPh3) 2Cl2 or Pd (PPh3) 4, and consumption is 0.01%-5% times of c mole dosage, and described solvent is that a kind of reaction formula in tetrahydrofuran (THF), DMF (DMF), dimethyl sulfoxide (DMSO) is as follows:
2) under anhydrous and oxygen-free condition, compound (e) is added in dry tetrahydrofuran (THF), and be cooled to-78 DEG C, slowly add 2.5mol/L(mol/L with syringe and be abbreviated as M) hexane solution of n-BuLi (n-Butyl Lithium), finish, at-78 DEG C after stirring reaction 2 ~ 3h, then add the tetrahydrofuran solution of a certain amount of trimethyltin chloride, return to room temperature after insulation reaction 0.5 ~ 1h, continue reaction 20 ~ 24h.Stopped reaction, removes excessive solvent and trimethyltin chloride under reduced pressure, obtains product (A); Wherein n-BuLi and chlorination trimethyltin chloride are 2.2 ~ 2.5 times of compound (e) consumption; Its reaction formula is as follows:
Compd B is bought in Receive triumphant scientific and technological Co., Ltd. in Suzhou.
The invention still further relates to the application of above-mentioned conjugated polymers in organic electroluminescence device, organic field effect tube, organic solar batteries device, organic light storage device, organic non-linear optical properties or organic laser.
Be specifically described with the preparation process of embodiment to conjugated polymers of the present invention below:
Embodiment 1
Conjugated polymers disclosed in the present embodiment is specially compound P1, and structural formula is as follows:
n＝5；
One, the preparation of compd A 1
1) in reaction flask, under nitrogen atmosphere, add 906mg (2.0mmol) 5,8-dibromo two thieno-[3 ', 2 ': 3,4 successively; 2 ' ', 3 ' ': 5,6] benzo [1,2-c] [1,2,5] selenium diazole (c1), 1.15g (2.2mmol) 3,6-bis-(dodecyl) thieno-[3,2-b] thiophene-2-boric acid (d1), 0.64g (6.0mmol) sodium carbonate, 0.23mg (0.0002mmol) Pd (PPh 3) 4, the tetrahydrofuran (THF) of 60ml drying.Reaction mixture, after 60 DEG C of stirring and refluxing reaction 24h, is cooled to room temperature, is poured into by reaction solution in distilled water, carry out cancellation reaction.Use dichloromethane extraction again, wash with saturated common salt after merging organic phase, filter after dry, revolve and steam except a large amount of organic solvent, compound (e1) is obtained through silicagel column separation and purification, eluent is ethyl acetate/petroleum ether=1/5(v/v), productive rate is 81%, MS (EI) m/z:1245 (M +); Reaction formula is as follows:
2) under anhydrous and oxygen-free condition, 2.49g (2.0mmol) compound (e1) is added in the tetrahydrofuran (THF) of 80ml drying, and be cooled to-78 DEG C, the hexane solution of 1.8ml (4.4mmol) 2.5M n-BuLi is slowly added with syringe, finish, at-78 DEG C after stirring reaction 2h, then add the tetrahydrofuran solution of 1.3ml (4.4mmol) tin chloride, return to room temperature after insulation reaction 0.5h, continue reaction 20h.Stopped reaction, removes excessive solvent and trimethyltin chloride under reduced pressure, obtains product (A1), productive rate 63%, MS (EI) m/z:1570 (M +); Its reaction formula is as follows:
Two, the preparation of conjugated polymers (P1)
Under nitrogen protection; by 4 of the compd A 1 of 3.45g (2.2mmol) and 0.59g (2.0mmol); 7-dibromo benzo [1; 2; 5] thiadiazoles (B) joins in the toluene of 80ml drying; bubbling 0.5h removes residual oxygen, then adds rapidly 0.23mg (0.0002mmol) Pd (PPh 3) 4catalyzer, bubbling 1h removes residual oxygen, and back flow reaction 24h at 120 DEG C, removes mixed solution under reduced pressure excessive toluene, then is added drop-wise in methyl alcohol and carries out sedimentation.By methanol wash after suction filtration, drier.Then successively by the column chromatography of aluminum oxide and the drip washing of chloroform, then steam removing organic solvent, then use suction filtration after methyl alcohol sedimentation, gained solid acetone surname extraction three days.Suction filtration after methyl alcohol sedimentation, is pumped through and obtains product P 1 night under vacuum pump again.
Molecular weight (GPC, THF, R.I): M n=6885, dispersion coefficient M w/ M n=2.7).
Embodiment 2
Conjugated polymers disclosed in the present embodiment is specially compound P2, and structural formula is as follows:
n＝60；
One, the preparation of compd A 2:
1) in reaction flask, under nitrogen atmosphere, add 906mg (2.0mmol) 5,8-dibromo two thieno-[3 ', 2 ': 3,4 successively; 2 ' ', 3 ' ': 5,6] benzo [1,2-c] [1,2,5] selenium diazole (c2), 0.44g (2.4mmol) thieno-[3,2-b] thiophene-2-boric acid (d2), 1.38g (10.0mmol) salt of wormwood, 115.6mg (0.1mmol) Pd (PPh 3) 4, the DMF of 70ml drying.Reaction mixture, after 78 DEG C of stirring reaction 36h, is cooled to room temperature, is poured into by reaction solution in distilled water, carries out cancellation reaction.Use dichloromethane extraction again, wash with saturated common salt after merging organic phase, filter after dry, revolve and steam except a large amount of organic solvent, compound (e2) is obtained through silicagel column separation and purification, eluent is ethyl acetate/petroleum ether=1/5(v/v), productive rate is 85%, MS (EI) m/z:572 (M +); Reaction formula is as follows:
2) under anhydrous and oxygen-free condition, 1.14g (2.0mmol) compound (e2) is added in the tetrahydrofuran (THF) of 60ml drying, and be cooled to-78 DEG C, the hexane solution of 2.0ml (5.0mmol) 2.5M n-BuLi is slowly added with syringe, finish, at-78 DEG C after stirring reaction 3h, then add the tetrahydrofuran solution of 1.5ml (5.0mmol) tin chloride, return to room temperature after insulation reaction 1h, continue reaction 24h.Stopped reaction, removes excessive solvent and trimethyltin chloride under reduced pressure, obtains product (A2), productive rate 63.6%, MS (EI) m/z:897 (M +); Its reaction formula is as follows:
Two, the preparation of conjugated polymers (P2)
Under argon shield; by 2.69g (3mmol) A2 and 0.68g (2.0mmol) 4; 7-dibromo benzo [1; 2; 5] thiadiazoles (B) joins in the tetrahydrofuran (THF) of 80ml drying; bubbling 0.5h removes residual oxygen, then adds rapidly 28mg (0.04mmol) Pd (PPh 3) 2cl 2catalyzer, bubbling 1h removes residual oxygen, and back flow reaction 36h at 60 DEG C, removes mixed solution under reduced pressure excessive tetrahydrofuran (THF), then is added drop-wise in methyl alcohol and carries out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Steam removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Molecular?weight(GPC,THF,R.I):Mn=10560,M w/M n=2.2）。
Embodiment 3
Conjugated polymers disclosed in the present embodiment is specially compound P3, and structural formula is as follows:
n＝30；
One, the preparation of compound A-13
1) in reaction flask, under nitrogen atmosphere, add 906mg (2.0mmol) 5,8-dibromo two thieno-[3 ', 2 ': 3,4 successively; 2 ' ', 3 ' ': 5,6] benzo [1,2-c] [1,2,5] selenium diazole (c3), 0.49g (2.3mmol) 3,6-thioxene also [3,2-b] thiophene-2-boric acid (d3), 2.61g (8.0mmol) cesium carbonate, the DMSO of 28.1mg (0.04mmol) Pd (PPh3) 2Cl2,60ml drying.Reaction mixture, after 80 DEG C of stirring reaction 72h, is cooled to room temperature, is poured into by reaction solution in distilled water, carries out cancellation reaction.Use dichloromethane extraction again, wash with saturated common salt after merging organic phase, filter after dry, revolve and steam except a large amount of organic solvent, compound (e3) is obtained through silicagel column separation and purification, eluent is ethyl acetate/petroleum ether=1/5(v/v), productive rate is 85%, MS (EI) m/z:628 (M +); Reaction formula is as follows:
2) under anhydrous and oxygen-free condition, 1.26g (2.0mmol) compound (e3) is added in the tetrahydrofuran (THF) of 60ml drying, and be cooled to-78 DEG C, the hexane solution of 1.9ml (4.8mmol) 2.5M n-BuLi is slowly added with syringe, finish, at-78 DEG C after stirring reaction 2.5h, then add the tetrahydrofuran solution of 1.4ml (4.8mmol) tin chloride, return to room temperature after insulation reaction 0.6h, continue reaction 22h.Stopped reaction, removes excessive solvent and trimethyltin chloride under reduced pressure, obtains product (A3), productive rate 64%, MS (EI) m/z:953 (M +); Its reaction formula is as follows:
Two, the preparation of conjugated polymers (P3)
Under argon gas and argon shield; by 2.29g (2.4mmol) compound A-13 and 0.59g (2.0mmol) 4; 7-dibromo benzo [1; 2; 5] thiadiazoles (B) joins in the DMF of 70ml drying; bubbling 0.5h removes residual oxygen, then adds rapidly 91.6mg (0.1mmol) Pd 2(dba) 3with 60.8mg (0.2mmol) P (o-Tol) 3catalyzer, bubbling 1h removes residual oxygen, and back flow reaction 72h at 80 DEG C, removes mixed solution under reduced pressure excessive DMF, then is added drop-wise in methyl alcohol and carries out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Steam removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Molecular?weight(GPC,THF,R.I):M n=22800,M w/M n=2.1）。
Embodiment 4
Conjugated polymers disclosed in the present embodiment is specially compound P4, and structural formula is as follows:
n＝15；
One, the preparation of compd A 4
1) in reaction flask, under nitrogen atmosphere, add 906mg (2.0mmol) 5,8-dibromo two thieno-[3 ', 2 ': 3,4 successively; 2 ' ', 3 ' ': 5,6] benzo [1,2-c] [1,2,5] selenium diazole (c4), 0.84g (2.3mmol) 3,6-dihexyl thieno-[3,2-b] thiophene-2-boric acid (d4), 2.61g (8.0mmol) cesium carbonate, 28.1mg (0.04mmol) Pd (PPh 3) 2cl 2, the DMSO of 60ml drying.Reaction mixture, after 80 DEG C of stirring reaction 30h, is cooled to room temperature, is poured into by reaction solution in distilled water, carries out cancellation reaction.Use dichloromethane extraction again, wash with saturated common salt after merging organic phase, filter after dry, revolve and steam except a large amount of organic solvent, compound (e4) is obtained through silicagel column separation and purification, eluent is ethyl acetate/petroleum ether=1/5(v/v), productive rate is 81%, MS (EI) m/z:908 (M +); Reaction formula is as follows:
2) under anhydrous and oxygen-free condition, 1.82g (2.0mmol) compound (e4) is added in the tetrahydrofuran (THF) of 60ml drying, and be cooled to-78 DEG C, the hexane solution of 1.9ml (4.8mmol) 2.5M n-BuLi is slowly added with syringe, finish, at-78 DEG C after stirring reaction 2.5h, then add the tetrahydrofuran solution of 1.4ml (4.8mmol) tin chloride, return to room temperature after insulation reaction 0.6h, continue reaction 22h.Stopped reaction, removes excessive solvent and trimethyltin chloride under reduced pressure, obtains product (A4), productive rate 61%, MS (EI) m/z:1234 (M +); Its reaction formula is as follows:
Two, the preparation of conjugated polymers (P4)
Under the protection of argon gas and nitrogen mixed gas; by 2.96g (2.4mmol) compd A 4 and 0.59g (2.0mmol) 4; 7-dibromo benzo [1; 2; 5] thiadiazoles (B) joins in the DMF of 75ml drying; bubbling 0.5h removes residual oxygen, then adds rapidly 91.6mg (0.1mmol) Pd 2(dba) 3/ 608mg (2mmol) P (o-Tol) 3catalyzer, bubbling 1h removes residual oxygen, and back flow reaction 30h at 80 DEG C, removes mixed solution under reduced pressure excessive DMF, then is added drop-wise in methyl alcohol and carries out sedimentation.Suction filtration, methanol wash, dry.Then by the column chromatography of aluminum oxide, chloroform drip washing.Steam removing organic solvent, methyl alcohol sedimentation.Suction filtration, gained solid acetone surname extraction three days.Methyl alcohol sedimentation, suction filtration.Be pumped through under vacuum pump and obtain product night.
Molecular?weight(GPC,THF,R.I):M n=62400,M w/M n=2.3）。
Embodiment 5
The present embodiment is organic solar batteries, and the conjugated polymers that its active coating adopts embodiment 1 obtained is as the electron donor material (representing with P1) of active coating.
Preparation method is:
1, select ito glass, wherein, ITO is anode, and glass is substrate; Ito glass, after ultrasonic cleaning, processes ITO surface with oxygen-Plasma; The tin indium oxide of ITO to be square resistance be 10-20 Ω;
2, adopt spin coating proceeding, on ITO on the surface spin coating, PEDOT:PSS(colon ": " represents mixing of mutually adulterating) as anode modification layer; PEDOT is poly-(3,4-Ethylenedioxy Thiophene), and PSS is poly-(styrene sulfonic acid);
3, adopt spin coating proceeding, using the conjugated polymers (P1) in the present embodiment 1 as electron donor material, PCBM, as electron acceptor material, prepares active coating on anode modification layer surface; Active coating is expressed as P1:PCBM, and colon is doping;
4, finally aluminium negative electrode is prepared on active coating surface by vacuum evaporation technology;
After after above-mentioned technique completes, namely obtain the organic solar batteries device in the present embodiment, as shown in Figure 1, the representation of this organic solar batteries device is: glass/ITO/PEDOT:PSS/P1:PCBM/Al; Wherein, brace represents laminate structure.
Embodiment 6
The present embodiment is organic electroluminescence device, and its luminescent layer adopts embodiment 2 to obtain conjugated polymers (representing with P2).
Fig. 2 is the structure iron of organic electroluminescence device, and its structure is followed successively by: ITO/P2/LiF/Al; Wherein, brace represents laminate structure.
Concrete preparation method is:
1, select ito glass, wherein, ITO is anode, and glass is substrate; Ito glass, after ultrasonic cleaning, processes ITO surface with oxygen-Plasma; The tin indium oxide of ITO to be square resistance be 10-20 Ω;
2, by spin coating proceeding, luminescent layer is prepared at ITO layer surface spin coating P2;
3, vacuum evaporation LiF on this luminescent layer again, as buffer layer;
4, last evaporation metal Al, as the negative electrode of device;
After above-mentioned technique completes, namely obtain the organic electroluminescence device in the present embodiment, as shown in Figure 2, its representation is: glass/ITO/P2/LiF/Al; Wherein, brace represents laminate structure.
Embodiment 7
The present embodiment is organic field effect tube, the conjugated polymers (representing with P3) that its organic semiconductor layer adopts embodiment 3 obtained.
As shown in Figure 3, this organic field effect tube comprises silicon substrate, insulation layer, organic semiconductor layer, source electrode and drain electrode.
The preparation method of this organic field effect tube is: adopt highly doped silicon chip Si as substrate, with the SiO that 500nm is thick 2as insulation layer, and with octadecyl trichlorosilane alkane (OTS), it is modified, then utilize spin coated technology that conjugated polymers (P3) obtained for embodiment 3 is prepared in the SiO of OTS modification 2above layer, finally form two electrodes respectively as source electrode S and drain electrode D, obtain organic field effect tube.
It should be noted that, conjugated polymers of the present invention also can be applicable in the other technologies fields such as organic light storage device, organic non-linear optical properties or organic laser.
Foregoing; be only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skill in the art are according to central scope of the present invention and spirit; can carry out corresponding flexible or amendment very easily, therefore protection scope of the present invention should be as the criterion with the protection domain required by claims.

Claims (10)

1. the conjugated polymers of following general formula (P):
Wherein, R is H or C 1~ C 12alkyl, n is the natural number between 5 ~ 60.
2. a preparation method for conjugated polymers, the method comprises the following steps:
A) following compd A and B is provided;
Compd A is
Compd B is
B) under atmosphere of inert gases, described compd A and described compd B are joined in organic solvent with mol ratio 1.1 ~ 1.5:1, catalyzer is added after dissolving, Stille coupling reaction is carried out 24 ~ 72 hours again at 60 ~ 120 DEG C, separating-purifying, obtains conjugated polymers (P);
Wherein, R is H or C 1~ C 12alkyl, n is the natural number between 5 ~ 60.
3. the preparation method of conjugated polymers according to claim 2, is characterized in that, described catalyzer is tetrakis triphenylphosphine palladium or two (triphenylphosphine) palladium chloride; The mol ratio of described catalyzer and described compd A is 0.0001 ~ 0.05:1.
4. the preparation method of conjugated polymers according to claim 2, it is characterized in that, described catalyzer is the mixture of organic palladium and organophosphorus ligand, the mol ratio of described organic palladium and organophosphorus ligand is 1:2 ~ 20, and the mol ratio of described catalyzer and described compd A is 0.0001 ~ 0.05:1.
5. the preparation method of conjugated polymers according to claim 4, is characterized in that, described organic palladium is three (dibenzalacetone) two palladium, and described organophosphorus ligand is three (o-methyl-phenyl-) phosphine.
6. the preparation method of conjugated polymers according to claim 2, is characterized in that, the rare gas element in described atmosphere of inert gases is one or both in nitrogen, argon gas.
7. the preparation method of conjugated polymers according to claim 2, is characterized in that, described organic solvent is the one in tetrahydrofuran (THF), DMF or toluene.
8. the preparation method of conjugated polymers according to claim 2, it is characterized in that, described separating-purifying step is as follows: the reaction solution obtained by described Stille coupling reaction is by removing excessive solvent under reduced pressure, be added drop-wise to again in methyl alcohol and carry out sedimentation, by methanol wash after suction filtration, successively by the column chromatography of aluminum oxide and the drip washing of chloroform after drying, steam removing organic solvent again, suction filtration after methyl alcohol sedimentation, the solid acetone of gained is carried out surname extraction, suction filtration after methyl alcohol sedimentation, obtains described conjugated polymers again.
9. the preparation method of conjugated polymers according to claim 2, is characterized in that, compd A adopts following steps to obtain:
1), under atmosphere of inert gases, in reaction flask, add structural formula is successively alkylating 5,8-dibromo two thieno-s [3 ', 2 ': 3,4 of N-; 2 ' ', 3 ' ': 5,6] benzo [1,2-d] [1,2,5] selenium diazole (c), structural formula is the boric acid derivatives (d) of thieno-[3,2-b] thiophene, carbonate, palladium catalyst, reaction solvent, reactant, after 60 ~ 120 DEG C of stirring and refluxing reaction 24 ~ 72h, is cooled to room temperature, reaction solution is poured in distilled water, carry out cancellation reaction, then use dichloromethane extraction, wash with saturated common salt after merging organic phase, dry filter, silicagel column separation and purification obtains structural formula and is
verbindung; Wherein, 5,8-dibromo two thieno-[3 ', 2 ': 3,4; 2 ' ', 3 ' ': 5,6] mol ratio of the boric acid derivatives of benzo [1,2-d] [1,2,5] selenium diazole and thieno-[3,2-b] thiophene is 1:1.1 ~ 1:1.2; Carbonate makes alkali, and consumption is 5,8-dibromo two thieno-[3 ', 2 ': 3,4; 2 ' ', 3 ~ 5 times of 3 ' ': 5,6] benzo [1,2-d] [1,2,5] selenium diazole consumption; Palladium catalyst is Pd (PPh 3) 2cl 2or Pd (PPh 3) 4, consumption is 0.01% ~ 5% times of c mole dosage, and described solvent is the one in tetrahydrofuran (THF), DMF, dimethyl sulfoxide (DMSO);
2) under anhydrous and oxygen-free condition, described Verbindung is added in dry tetrahydrofuran (THF), and is cooled to-78 DEG C, slowly add the hexane solution of 2.5mol/L n-Butyl Lithium with syringe, finish, at-78 DEG C after stirring reaction 2 ~ 3h, then add the tetrahydrofuran solution of a certain amount of trimethyltin chloride, after insulation reaction 0.5 ~ 1h, return to room temperature, continue reaction 20 ~ 24h, stopped reaction, removes excessive solvent and trimethyltin chloride under reduced pressure, obtains described compd A; Wherein, n-Butyl Lithium and chlorination trimethyltin chloride are 2.2 ~ 2.5 times of described Verbindung consumption.
10. the application of the conjugated polymers described in an any one of claim 1 to 9 in organic electroluminescence device, organic field effect tube, organic solar batteries device, organic light storage device, organic non-linear optical properties or organic laser.
CN201310207006.1A 2013-05-29 2013-05-29 Conjugated polymer, preparation method and applications thereof Pending CN104211921A (en)

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