CN104211910A - Conjugated polymer, preparation method and applications thereof - Google Patents
Conjugated polymer, preparation method and applications thereof Download PDFInfo
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- 0 CCC(*)(c1c(-c(c(C)c2)cc3c2c([s]c(Br)c2)c2[n]3)[s]c(BrC)c1)I Chemical compound CCC(*)(c1c(-c(c(C)c2)cc3c2c([s]c(Br)c2)c2[n]3)[s]c(BrC)c1)I 0.000 description 4
- YVFXJPBZGXLIPW-UHFFFAOYSA-N Brc1c(-c(cc(c(-c([s]cc2)c2Br)c2)Br)c2Br)[s]cc1 Chemical compound Brc1c(-c(cc(c(-c([s]cc2)c2Br)c2)Br)c2Br)[s]cc1 YVFXJPBZGXLIPW-UHFFFAOYSA-N 0.000 description 2
- FZKDKYNURJDDNA-UHFFFAOYSA-N CCCCCCCC[n]1c(cc2c([s]cc3)c3[n](CCCCCCCC)c2c2)c2c2c1cc[s]2 Chemical compound CCCCCCCC[n]1c(cc2c([s]cc3)c3[n](CCCCCCCC)c2c2)c2c2c1cc[s]2 FZKDKYNURJDDNA-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention relates to a conjugated polymer represented by the formula (P), wherein the R1 represents an alkyl group with a carbon number of 1 to 16, the R2 represents an alkyl group with a carbon number of 1 to 16, the R3 and R4 are respectively represent an H atom or an alkyl group with a carbon number of 1 to 12, and n is a natural number in a range of 5 to 60. The invention also relates to a preparation method and applications of the conjugated polymer. Compared to the prior art, pyrroloindolodithiophene derivatives taken as the donor unit and a strong acceptor unit (furanopyrroledione) are bridged and copolymerized through thiophene, thus the energy gap of the conjugated copolymer is reduced through the interactive reactions (electron pushing and pulling effect) between the acceptor unit and the donor unit, and the light absorption range of the material is greatly enlarged. Through selecting the novel donor unit and acceptor unit, a D-pi-A type conjugated polymer containing a unit of pyrroloindolodithiophene-thiophene-selenolopyrroledione is developed.
Description
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.
Pyrroles's indoles 1,4-Dithiapentalene class unit is the electron donor material that a class is strong.Pyrroles's indoles 1,4-Dithiapentalene class modular construction is unique-and it has a kind of structural unit of keystone ring pentacene.This structure has large conjugate planes, significantly reduces on the one hand the bandwidth of polymkeric substance, and this coplanar structure makes current carrier shift to become between molecular skeleton and be more prone on the other hand, substantially increases carrier mobility.In this trapezoidal conjugated structure unit of pentacene, introduce the heteroatoms such as nitrogen, sulphur, significantly can change band gap and the photo absorption performance of polymer materials.Wherein, N-alkylation is conducive to the solvability improving monomer, thus improves Drawing abillity.Meanwhile, due to its this rigid planar structure, make it have good thermostability and environmental stability, therefore this kind of heterocycle pentacene is the up-and-coming material of a class, and it is extensively studied in the application in the fields such as organic electronic.
Furo pyrroledione unit is the derivative of Thienopyrroles diketone, is too to have the excellent in body unit of strong electron-withdrawing power as a kind of, and the application in photoelectric material widely.Compound containing furo pyrroledione unit has high electronic transport property, excellent electrochemical reduction character etc.Meanwhile, furo pyrroledione unit has stronger modifiability, and the introducing of alkyl in atom N also can improve its solvability effectively.Therefore, it is at Organic Light Emitting Diode, has a wide range of applications in the photoelectric material such as organic solar batteries, field-effect transistor.
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
1for C
1~ C
16alkyl, R
2for C
1~ C
16alkyl, R
3, R
4be respectively 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 ~ 1.5, 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
1for C
1~ C
16alkyl, R
2for C
1~ C
16alkyl, R
3, R
4be respectively 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) 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes) are synthesized
Under atmosphere of inert gases, in reaction flask, add lithium chloride successively, the bromo-Isosorbide-5-Nitrae-diiodo-benzene (a) of 2,5-bis-, palladium catalyst, cuprous chloride, 3 bromo thiophene class tin compound (b), reaction solvent; After reactant at room temperature stirs 1 ~ 2h, then react 3 ~ 4h at being warming up to 50-55 DEG C; Be cooled to room temperature, the solids that reaction generates obtains crude product 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c) after filtering; Wherein, described 2,5-bis-bromo-1,4-diiodo-benzene (a) is 1:1.1 ~ 1.5 with the mol ratio of bromo-2-tin trimethyl thiophene (b) of 3-, 2,5-bis-bromo-1, the mol ratio of 4-diiodo-benzene and lithium chloride, cuprous chloride is respectively 1:6 ~ 1:6.2 and 1:5 ~ 1:5.2, and palladium catalyst is Pd (PPh
3)
2cl
2or Pd (PPh
3)
4, consumption is 0.01%-5% times of 2,5-bis-bromo-Isosorbide-5-Nitrae-diiodo-benzene mole dosage, and solvent is the one in tetrahydrofuran (THF), DMF (DMF), toluene;
2) N-alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative is synthesized
Under atmosphere of inert gases, successively by 2, 2 '-(2, 5-bis-bromo-1, 4-phenyl) two (3 bromo thiophene) (c), sodium tert-butoxide, 2, 2 '-bis-(diphenyl phosphine)-1, 1 '-dinaphthalene (BINAP), after alkylamine and palladium catalyst join and dissolve in solvent, stirring and refluxing reaction 2 ~ 3h, be cooled to room temperature, filter and remove reaction solids, organic phase is obtained after the filtrate extraction obtained, organic phase is after saturated common salt washing, dry, filter, revolve and steam except after a large amount of organic solvent, alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative (d) of N-is obtained through silica gel column chromatography separating-purifying, wherein, 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes) are 1:3 ~ 4 with the mol ratio of amine, sodium tert-butoxide and BINAP are respectively 2,5 ~ 8 times of 2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) consumption, 0.2 ~ 0.3 times, described palladium catalyst is Pd (PPh
3)
2cl
2, Pd
2(dba)
3or Pd (PPh
3)
4, consumption is 5%-10% times of 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) mole dosage, and solvent is the one in p-Xylol, toluene, preferred p-Xylol,
3) bromination of N-alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative is synthesized
Under atmosphere of inert gases, the tetrahydrofuran (THF) of pyrroles's indoles 1,4-Dithiapentalene analog derivative (d) or DMF solution are cooled to-78 DEG C, are slowly added dropwise in reaction flask from constant pressure funnel after N-bromo-succinimide tetrahydrofuran (THF) or DMF are dissolved; The mol ratio of pyrroles's indoles 1,4-Dithiapentalene analog derivative and N-bromo-succinimide is 1:2.2 ~ 3; Dropwise, continue stirring reaction 0.5 ~ 1h, carry out cancellation reaction with water, after reaction solution dichloromethane extraction, dry, obtain described compd A through silica gel column chromatography separating-purifying.
Compd B prepare reference Polymer52 (2011) 415-421.
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, in conjugated polymers of the present invention, pyrroles's indoles 1,4-Dithiapentalene analog derivative is passed through the copolymerization of selenophen overseas Chinese federation as donor monomer and the strong body unit furo pyrroledione that is subject to, by giving the interaction of this " pushing away-La electronics " between acceptor, reduce the energy gap of conjugated polymers, substantially increase the light abstraction width of material.Therefore, the present invention by select these two kinds novel to body with by body unit, develop containing the such class D – п-A type conjugated polymers of pyrroles's indoles 1,4-Dithiapentalene-selenophen-furo pyrroledione unit.
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
1for C
1~ C
16alkyl, R
2for C
1~ C
16alkyl, R
3, R
4be respectively 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 ~ 1.5, 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
1for C
1~ C
16alkyl, R
2for C
1~ C
16alkyl, R
3, R
4be respectively 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 conjugated polymers again.
In addition, the preparation scheme of compd A, comprises the steps:
1) 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes) are synthesized
Under atmosphere of inert gases (rare gas element comprises nitrogen and argon gas etc.), in reaction flask, add lithium chloride successively, the bromo-Isosorbide-5-Nitrae-diiodo-benzene (a) of 2,5-bis-, palladium catalyst, cuprous chloride, 3 bromo thiophene class tin compound (b), reaction solvent.After reactant at room temperature stirs 1 ~ 2h, then react 3 ~ 4h at being warming up to 50-55 DEG C.Be cooled to room temperature, the solids that reaction generates obtains crude product c after filtering, wherein said 2,5-bis-bromo-1,4-diiodo-benzene (a) is 1:1.1 ~ 1:1.5,2,5-bis-bromo-1 with the mol ratio of bromo-2-tin trimethyl thiophene (b) of 3-, 4-diiodo-benzene (a) is respectively 1:6 ~ 1:6.2 and 1:5 ~ 1:5.2 with the mol ratio of lithium chloride, cuprous chloride, and palladium catalyst is Pd (PPh
3)
2cl
2or Pd (PPh
3)
4, consumption is 0.01%-5% times of a mole dosage, and solvent is the one in tetrahydrofuran (THF), DMF, toluene.
2) N-alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative (Buchwald-Hartwig linked reaction) is synthesized
Under atmosphere of inert gases, add 2 successively, 2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c), sodium tert-butoxide, 2,2 '-bis-(diphenyl phosphine)-1,1 '-dinaphthalene (BINAP), alkylamine and solvent, palladium catalyst, solvent.Stirring and refluxing reaction 2 ~ 3h, be cooled to room temperature, filter and remove reaction solids, organic phase is obtained after the filtrate extraction obtained, organic phase is after saturated common salt washing, dry, filters, revolve and steam except after a large amount of organic solvent, obtain alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative (d) of N-through silica gel column chromatography separating-purifying.Wherein, 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c) are 1:3 ~ 4 with the mol ratio of amine; Sodium tert-butoxide and BINAP are respectively 5 ~ 8 times of compound (c) consumption, 0.2 ~ 0.3 times; Described palladium catalyst is Pd (PPh
3)
2cl
2, Pd
2(dba)
3or Pd (PPh
3)
4, consumption is 5%-10% times of c mole dosage, and solvent is the one in p-Xylol/toluene, preferred p-Xylol.
3) bromination (A) of N-alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative is synthesized
(nitrogen is comprised in atmosphere of inert gases, argon gas etc.), the tetrahydrofuran (THF) of pyrroles's indoles 1,4-Dithiapentalene analog derivative (d)/DMF solution is cooled to-78 DEG C, after being dissolved by N-bromo-succinimide (NBS) tetrahydrofuran (THF)/DMF, from constant pressure funnel, is slowly added dropwise to (mol ratio of d and NBS is 1:2.2 ~ 3) in reaction flask.Dropwise, continue stirring reaction 0.5 ~ 1h, to go out reaction with shrend.After reaction solution dichloromethane extraction, dry, obtain compd A through silica gel column chromatography separating-purifying.
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:
One, the preparation of compd A 1
1) synthesis of 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes)
Under nitrogen protection, in reaction flask, add 2.54g (60mmol) lithium chloride successively, the bromo-Isosorbide-5-Nitrae-diiodo-benzene (a) of 4.8g (10mmol) 2,5-bis-, 287.5mg (0.25mmol) Pd (PPh
3)
4, 5g (50mmol) cuprous chloride, bromo-2-tin trimethyl thiophene (b) of 3.59g (11mmol) 3-, 60ml tetrahydrofuran (THF).After reactant at room temperature stirs 1h, then react 3h at being warming up to 50 DEG C.Be cooled to room temperature, the solids that reaction generates obtains crude product c, i.e. 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes), productive rate 40%, MS (EI) m/z:558 (M after filtering
+);
2) synthetic compound d1
Under argon shield; add 558mg (1mmol) 2 successively; 2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c); 768mg (8mmol) sodium tert-butoxide; 124mg (0.2mmol) 2,2 '-bis-(diphenyl phosphine)-1,1 '-dinaphthalene (BINAP); 724.5mg (3mmol) 2-butyl lauryl amine, 57.8mg (0.05mmol) Pd (PPh
3)
4with 70ml p-Xylol.Stir and be heated to 138 DEG C of back flow reaction 2h, being cooled to room temperature, filtering and remove reaction solids, after the filtrate dichloromethane extraction obtained, obtain organic phase, after saturated common salt washing, using MgSO
4drying, filters, and revolve and steam except after a large amount of organic solvent, obtain compound d1 through silica gel column chromatography separating-purifying, eluent is normal hexane/methylene dichloride=8/1(v/v), productive rate 70%, MS (EI) m/z:717 (M
+);
3) synthon compd A 1
Under argon atmosphere, 717mg (1mmol) compound (d1) is added in 50ml anhydrous tetrahydro furan, solution is also cooled to-78 DEG C by stirring and dissolving, is slowly added dropwise in reaction flask after being dissolved by 391.6mg (2.2mmol) NBS tetrahydrofuran (THF) from constant pressure funnel.Dropwise, continue stirring reaction 0.5h, with a small amount of distilled water cancellation reaction.After reaction solution dichloromethane extraction, organic phase is through MgSO
4drying, filters, and revolve and steam except a large amount of solvent, obtain compd A 1 through silica gel column chromatography separating-purifying, eluent is normal hexane, productive rate 40%, MS (EI) m/z:875 (M
+).
Two, the preparation of conjugated polymers (P1)
Under nitrogen protection; by 1.75g (2.0mmol) compound (A1) and 2.36g (2.2mmol) 1; 3-bis-(4-dodecyl-5-tin trimethyl-2-selenophen)-5-methyl furan also [3; 4-c] pyrroles-4; 6-diketone (B1) 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 110 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): the M of above-mentioned obtained conjugated polymers
n=7295, dispersion coefficient M
w/ M
n=2.3).
Embodiment 2
Conjugated polymers disclosed in the present embodiment is specially compound P2, and structural formula is as follows:
One, the preparation of compd A 2:
1) 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes) are synthesized
Under nitrogen protection, in reaction flask, add 2.63g (62mmol) lithium chloride successively, the bromo-Isosorbide-5-Nitrae-diiodo-benzene (a) of 4.8g (10mmol) 2,5-bis-, 0.7mg (0.001mmol) Pd (PPh
3)
2cl
2, 5.15g (52mmol) cuprous chloride, bromo-2-tin trimethyl thiophene (b) of 4.89g (15mmol) 3-, 60mlDMF.After reactant at room temperature stirs 2h, then react 4h at being warming up to 55 DEG C.Be cooled to room temperature, the solids that reaction generates obtains crude product c, i.e. 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes), productive rate 39%, MS (EI) m/z:558 (M after filtering
+); (reaction formula is shown in embodiment 1)
2) synthetic compound d2
Under nitrogen protection; add 558mg (1mmol) 2 successively; 2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c); 480mg (5mmol) sodium tert-butoxide; 187mg (0.3mmol) 2,2 '-bis-(diphenyl phosphine)-1,1 '-dinaphthalene (BINAP); 404mg (4mmol) hexylamine, 70.2mg (0.1mmol) Pd (PPh
3)
2cl
2with 70ml p-Xylol.Stir and be heated to 138 DEG C of back flow reaction 3h, being cooled to room temperature, filtering and remove reaction solids, after the filtrate dichloromethane extraction obtained, obtain organic phase, after saturated common salt washing, using MgSO
4drying, filters, and revolve and steam except after a large amount of organic solvent, obtain compound d2 through silica gel column chromatography separating-purifying, eluent is normal hexane/methylene dichloride=10/1, productive rate 72%, MS (EI) m/z:437 (M
+);
3) synthetic compound A2
Under argon atmosphere, 437mg (1mmol) compound (d2) is added in the dry DMF of 50ml, solution is also cooled to-78 DEG C by stirring and dissolving, is slowly added dropwise in reaction flask after being dissolved by 534mg (3mmol) NBS DMF from constant pressure funnel.Dropwise, continue stirring reaction 1h, carry out cancellation reaction with a small amount of distilled water.After reaction solution dichloromethane extraction, organic phase is through MgSO
4drying, filters, and revolve and steam except a large amount of solvent, obtain compd A 2 through silica gel column chromatography separating-purifying, eluent is normal hexane, productive rate 41.6%, MS (EI) m/z:594 (M
+).
Two, the preparation of conjugated polymers (P2):
Under argon shield; by 1.19g (2.0mmol) compound (A2) and 2.0g (2.4mmol) 1; 3-bis-(5-tin trimethyl-2-selenophen)-5-octyl group furo [3; 4-c] pyrroles-4; 6-diketone (B2) 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 48h at 80 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.
The Molecular weight (GPC, THF, R.I) of above-mentioned obtained conjugated polymers: Mn=56400, M
w/ M
n=2.1).
Embodiment 3
Conjugated polymers disclosed in the present embodiment is specially compound P3, and structural formula is as follows:
One, the preparation of compound A-13
1) 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes) are synthesized
Under nitrogen protection, in reaction flask, add 2.59g (61mmol) lithium chloride successively, the bromo-Isosorbide-5-Nitrae-diiodo-benzene (a) of 4.8g (10mmol) 2,5-bis-, 578mg (0.5mmol) Pd (PPh
3)
4, 5.05g (51mmol) cuprous chloride, bromo-2-tin trimethyl thiophene (b) of 3.91g (12mmol) 3-, 60ml toluene.After reactant at room temperature stirs 1.5h, then react 3.5h at being warming up to 52 DEG C.Be cooled to room temperature, the solids that reaction generates obtains crude product c, i.e. 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes), productive rate 42%, MS (EI) m/z:558 (M after filtering
+); (reaction formula is shown in embodiment 1)
2) synthetic compound d3
Under nitrogen protection; add 558mg (1mmol) 2 successively; 2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c); 672mg (7mmol) sodium tert-butoxide; 156mg (0.25mmol) 2,2 '-bis-(diphenyl phosphine)-1,1 '-dinaphthalene (BINAP); 108.5mg (3.5mmol) methylamine, 73.3mg (0.08mmol) Pd2 (dba) 3 and 70ml toluene.Stir and be heated to 112 DEG C of back flow reaction 2.5h, being cooled to room temperature, filtering and remove reaction solids, after the filtrate dichloromethane extraction obtained, obtain organic phase, after saturated common salt washing, using MgSO
4drying, filters, and revolve and steam except after a large amount of organic solvent, obtain compound d3 through silica gel column chromatography separating-purifying, eluent is normal hexane/methylene dichloride=10/1, productive rate 71.2%, MS (EI) m/z:296 (M
+);
2) synthetic compound A3
Under nitrogen atmosphere, 296mg (1mmol) compound (d3) is added in 40ml dry tetrahydrofuran, solution is also cooled to-78 DEG C by stirring and dissolving, is slowly added dropwise in reaction flask after being dissolved by 445mg (2.5mmol) NBS tetrahydrofuran (THF) from constant pressure funnel.Dropwise, continue stirring reaction 0.6h, with a small amount of distilled water cancellation reaction.After reaction solution dichloromethane extraction, organic phase is through MgSO
4drying, filters, and revolve and steam except a large amount of solvent, obtain compound A-13 through silica gel column chromatography separating-purifying, eluent is normal hexane, productive rate 40.2%, MS (EI) m/z:454 (M
+).
Two, the preparation of conjugated polymers (P3)
Under argon gas and argon shield; by 0.91g (2.0mmol) compound (A3) and 3.34g (3.0mmol) 1; 3-bis-(4-hexyl-5-tin trimethyl-2-selenophen)-5-(2-hexyl certain herbaceous plants with big flowers base) furo [3; 4-c] pyrroles-4; 6-diketone (B3) joins in the THF of 100ml 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 60 DEG C, removes mixed solution under reduced pressure excessive 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): the M of above-mentioned obtained conjugated polymers
n=34200, M
w/ M
n=2.2).
Embodiment 4
Conjugated polymers disclosed in the present embodiment is specially compound P4, and structural formula is as follows:
One, the preparation of compd A 4
1) under protection of ammonia, by 1.2g (5.0mmol) 2-dimethoxy phosphono-4, 5-dimethyl-1, the 50ml anhydrous tetrahydrofuran solution of 3-bis-mercaptan (b4) is cooled to-78 DEG C, slowly add the cyclohexane solution (3.0mmol) of 2.0ml1.5M lithium diisopropyl amido LDA, finish, at-78 DEG C after stirring reaction 3h, add 0.46g (2.1mmol) benzo [1 again, 2-b:4, 5-b '] two thiophene-4, the 10ml anhydrous tetrahydrofuran solution of 8-diketone (a) carries out Wittig-Horner reaction, room temperature is returned to after insulation reaction 0.5h, continue reaction 12h, stopped reaction.Revolve except excessive tetrahydrofuran (THF), the crude on silica gel column chromatographic isolation and purification obtained, obtain product 4,8-bis-(4,5-dimethyl-1,3-bis-mercaptan-2-aldehyde) benzo [1,2-b:4,5-b '] two thiophene (c4); Eluent is normal hexane/methylene dichloride=4/1, productive rate 53%, MS (EI) m/z:449 (M
+); Its reaction formula is as follows:
2) synthetic compound d4
Under argon shield; add 558mg (1mmol) 2 successively; 2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c); 768mg (8mmol) sodium tert-butoxide; 124mg (0.2mmol) 2,2 '-bis-(diphenyl phosphine)-1,1 '-dinaphthalene (BINAP); 387mg (3mmol) octylame, 57.8mg (0.05mmol) Pd (PPh
3)
4with 70ml p-Xylol.Stir and be heated to 138 DEG C of back flow reaction 2h, being cooled to room temperature, filtering and remove reaction solids, after the filtrate dichloromethane extraction obtained, obtain organic phase, after saturated common salt washing, using MgSO
4drying, filters, and revolve and steam except after a large amount of organic solvent, obtain compound d1 through silica gel column chromatography separating-purifying, eluent is normal hexane/methylene dichloride=10/1, productive rate 72%, MS (EI) m/z:493 (M
+);
3) synthetic compound A4
Under nitrogen atmosphere, 493mg (1mmol) compound (d4) is added in 45ml dry tetrahydrofuran, solution is also cooled to-78 DEG C by stirring and dissolving, is slowly added dropwise in reaction flask after being dissolved by 391.6mg (2.2mmol) NBS tetrahydrofuran (THF) from constant pressure funnel.Dropwise, continue stirring reaction 0.5h, with a small amount of distilled water cancellation reaction.After reaction solution dichloromethane extraction, organic phase is through MgSO
4drying, filters, and revolve and steam except a large amount of solvent, obtain compd A 4 through silica gel column chromatography separating-purifying, eluent is normal hexane, productive rate 45%, MS (EI) m/z:651 (M
+).
Two, the preparation of conjugated polymers (P4)
Under the protection of argon gas and nitrogen mixed gas; by 1.30g (2.0mmol) compound (A4) and 1.89g (2.2mmol) 1; 3-bis-(3-methyl-5-tin trimethyl-2-selenophen)-5-octyl group furo [3; 4-c] pyrroles-4; 6-diketone (B4) joins in the THF 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 36h at 60 DEG C, removes mixed solution under reduced pressure excessive 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): the M of above-mentioned obtained conjugated polymers
n=15810, M
w/ M
n=2.2).
Embodiment 5
Conjugated polymers disclosed in the present embodiment is specially compound P5, and structural formula is as follows:
One, the preparation of compound A-45
The preparation of compound A-45 is identical with the step one of embodiment 4.
Two, the preparation of conjugated polymers (P5)
Under the protection of argon gas and nitrogen mixed gas; by 1.30g (2.0mmol) compound (A5) and 1.89g (2.2mmol) 1; 3-bis-(4-methyl-5-tin trimethyl-2-selenophen)-5-octyl group furo [3; 4-c] pyrroles-4; 6-diketone (B5) joins in the THF 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 48h at 60 DEG C, removes mixed solution under reduced pressure excessive 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): the M of above-mentioned obtained conjugated polymers
n=18432, M
w/ M
n=2.2).
Embodiment 6
Conjugated polymers disclosed in the present embodiment is specially compound P6, and structural formula is as follows:
Two, the preparation of compd A 6
The preparation of compd A 6 is identical with the step one of embodiment 4.
Two, the preparation of conjugated polymers (P6)
Under the protection of argon gas and nitrogen mixed gas; by 1.30g (2.0mmol) compound (A6) and 2.20g (2.2mmol) 1; 3-bis-(3-hexyl-5-tin trimethyl-2-selenophen)-5-octyl group furo [3; 4-c] pyrroles-4; 6-diketone (B6) joins in the THF 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 48h at 60 DEG C, removes mixed solution under reduced pressure excessive 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): the M of above-mentioned obtained conjugated polymers
n=23280, M
w/ M
n=2.3).
Embodiment 7
Conjugated polymers disclosed in the present embodiment is specially compound P7, and structural formula is as follows:
Three, the preparation of compd A 7
The preparation of compd A 7 is identical with the step one of embodiment 4.
Two, the preparation of conjugated polymers (P7)
Under the protection of argon gas and nitrogen mixed gas; by 1.30g (2.0mmol) compound (A7) and 2.57g (2.2mmol) 1; 3-bis-(3-dodecyl-5-tin trimethyl-2-selenophen)-5-octyl group furo [3; 4-c] pyrroles-4; 6-diketone (B7) joins in the THF 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 48h at 60 DEG C, removes mixed solution under reduced pressure excessive 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): the M of above-mentioned obtained conjugated polymers
n=29326, M
w/ M
n=2.0).
Embodiment 8
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 9
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 10
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
1for C
1~ C
16alkyl, R
2for C
1~ C
16alkyl, R
3, R
4be respectively 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 ~ 1.5, 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
1for C
1~ C
16alkyl, R
2for C
1~ C
16alkyl, R
3, R
4be respectively 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) 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes) are synthesized
Under atmosphere of inert gases, in reaction flask, add lithium chloride successively, the bromo-Isosorbide-5-Nitrae-diiodo-benzene (a) of 2,5-bis-, palladium catalyst, cuprous chloride, 3 bromo thiophene class tin compound (b), reaction solvent; After reactant at room temperature stirs 1 ~ 2h, then react 3 ~ 4h at being warming up to 50-55 DEG C; Be cooled to room temperature, the solids that reaction generates obtains crude product 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) (c) after filtering; Wherein, described 2,5-bis-bromo-1,4-diiodo-benzene (a) is 1:1.1 ~ 1.5 with the mol ratio of bromo-2-tin trimethyl thiophene (b) of 3-, 2,5-bis-bromo-1, the mol ratio of 4-diiodo-benzene and lithium chloride, cuprous chloride is respectively 1:6 ~ 1:6.2 and 1:5 ~ 1:5.2, and palladium catalyst is Pd (PPh
3)
2cl
2or Pd (PPh
3)
4, consumption is 0.01%-5% times of 2,5-bis-bromo-Isosorbide-5-Nitrae-diiodo-benzene mole dosage, and solvent is the one in tetrahydrofuran (THF), DMF, toluene;
2) N-alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative is synthesized
Under atmosphere of inert gases, successively by 2, 2 '-(2, 5-bis-bromo-1, 4-phenyl) two (3 bromo thiophene) (c), sodium tert-butoxide, 2, 2 '-bis-(diphenyl phosphine)-1, 1 '-dinaphthalene (BINAP), after alkylamine and palladium catalyst join and dissolve in solvent, stirring and refluxing reaction 2 ~ 3h, be cooled to room temperature, filter and remove reaction solids, organic phase is obtained after the filtrate extraction obtained, organic phase is after saturated common salt washing, dry, filter, revolve and steam except after a large amount of organic solvent, alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative (d) of N-is obtained through silica gel column chromatography separating-purifying, wherein, 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophenes) are 1:3 ~ 4 with the mol ratio of amine, sodium tert-butoxide and 2,2 '-bis-(diphenyl phosphine)-1,1 '-dinaphthalene is respectively 2,5 ~ 8 times of 2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) consumption, 0.2 ~ 0.3 times, described palladium catalyst is Pd (PPh
3)
2cl
2, Pd
2(dba)
3or Pd (PPh
3)
4, consumption is 5%-10% times of 2,2 '-(the bromo-Isosorbide-5-Nitrae-phenyl of 2,5-bis-) two (3 bromo thiophene) mole dosage, and solvent is the one in p-Xylol, toluene,
3) bromination of N-alkylating pyrroles's indoles 1,4-Dithiapentalene analog derivative is synthesized
Under atmosphere of inert gases, by the tetrahydrofuran (THF) of pyrroles's indoles 1,4-Dithiapentalene analog derivative (d) or N, dinethylformamide solution is cooled to-78 DEG C, slowly be added dropwise in reaction flask from constant pressure funnel after N-bromo-succinimide tetrahydrofuran (THF) or DMF are dissolved; The mol ratio of pyrroles's indoles 1,4-Dithiapentalene analog derivative and N-bromo-succinimide is 1:2.2 ~ 3; Dropwise, continue stirring reaction 0.5 ~ 1h, carry out cancellation reaction with water, after reaction solution dichloromethane extraction, dry, obtain described compd A through silica gel column chromatography separating-purifying.
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.
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|---|---|---|---|---|
| CA2625306A1 (en) * | 2008-03-11 | 2009-09-11 | National Research Council Of Canada | Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers |
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| WO2012079675A2 (en) * | 2010-12-17 | 2012-06-21 | Merck Patent Gmbh | Conjugated polymers |
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2013
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| CA2625306A1 (en) * | 2008-03-11 | 2009-09-11 | National Research Council Of Canada | Electron acceptors-cored regioregular oligothiophenes as building blocks for soluble low band-gap conjugated polymers |
| CN102344550A (en) * | 2010-07-30 | 2012-02-08 | 海洋王照明科技股份有限公司 | Perylenetetracarboxylic diimide copolymer containing thiophenepyrrole dione unit, preparation method thereof and application thereof |
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