CN103319694B - Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application - Google Patents

Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application Download PDF

Info

Publication number
CN103319694B
CN103319694B CN201310217355.1A CN201310217355A CN103319694B CN 103319694 B CN103319694 B CN 103319694B CN 201310217355 A CN201310217355 A CN 201310217355A CN 103319694 B CN103319694 B CN 103319694B
Authority
CN
China
Prior art keywords
phenanthridines
ketone
pyrido
polymer
constituted
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CN201310217355.1A
Other languages
Chinese (zh)
Other versions
CN103319694A (en
Inventor
苏仕健
刘明
曹镛
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
South China University of Technology SCUT
Original Assignee
South China University of Technology SCUT
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by South China University of Technology SCUT filed Critical South China University of Technology SCUT
Priority to CN201310217355.1A priority Critical patent/CN103319694B/en
Publication of CN103319694A publication Critical patent/CN103319694A/en
Application granted granted Critical
Publication of CN103319694B publication Critical patent/CN103319694B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/549—Organic PV cells
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Landscapes

  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention discloses the conjugated polymer containing pyrido phenanthridines-5-ketone and preparation and application thereof, belong to the novel polymer field of photoelectron material and device.The present invention carries out Suzuki coupling or Stille coupling copolymerization respectively by selecting multiple conjugation fragrant monomer with the monomer containing pyrido phenanthridines-5-ketone, it is thus achieved that containing the conjugated polymer of pyrido phenanthridines-5-ketone.New copolymer prepared by the present invention, has fluorescence, and sunlight is had absorbability, therefore can be applicable to make polymer LED device and the active layer of polymer field effect transistor and polymer solar cells.

Description

Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application
Technical field
The present invention relates to a kind of new polymer being applied to photoelectron material and devices field, particularly to the Optical Properties of Novel Conjugated containing pyrido phenanthridines-5-ketone and preparation and application thereof.
Background technology
Since Japanese Scientists Hideki Shirakawa in 1977 finds polyacetylene conduction, this conducting polymer being referred to as " forth generation macromolecule " material has attracted numerous scientist to study with its prominent photoelectric properties.The advantages such as conducting polymer is compared with the inorganic material with same or like purposes, has density low, easily processes, and the synthesis range of choice is wide.Due to the conjugate property of this kind of material structure, enable it to transmission electric charge, stimulated luminescence such that it is able to or potentially possible be applied on many electronics or opto-electronic device, for instance include polymer LED, photovoltaic cell, field effect transistor etc..Potential application prospect and be widely applied field and promote scientist competitively to study this kind of conjugated material with photoelectric activity, including the little molecule of multiple conjugated structure, and polyacetylene, polypyrrole, polythiophene, polyaniline, polyfluorene, polycarbazole etc..Research worker has been working hard seek to improve polymer LED, photovoltaic cell, the method for field effect transistor performance, and material is one of most important factor.So many research groups are devoted to exploitation and have a high-quantum efficiency always, high color purity, the light emitting polymer that long-time stability are good, and visible-range absorption bands width, polymer that carrier mobility is high.Realize these targets, it is necessary to develop more Optical Properties of Novel Conjugated material.Pyrido phenanthridines-5-ketone is a kind of novel monomeric, has the advantages that flatness is good, modifiability is strong, preparation method is simple, cost is comparatively cheap, has certain application potential in novel organic semi-conductor field.
Summary of the invention
It is an object of the invention to the shortcoming overcoming prior art to exist, it is provided that containing the polymer of pyrido phenanthridines-5-ketone, conjugated polymer has fluorescence, and sunlight is had absorbability.
The preparation method that another object of the present invention is to provide the described conjugated polymer containing pyrido phenanthridines-5-ketone.
It is still another object of the present invention to provide the application in polymer LED, polymer field effect transistor and polymer solar cells of the described conjugated polymer containing pyrido phenanthridines-5-ketone.
The conjugated polymer containing pyrido phenanthridines-5-ketone of the present invention has the structure shown in following formula I c or I d:
Wherein, R is C1～C24Alkyl；Ar is the one in following conjugate unit: the conjugate unit of alkyl replacement, the conjugate unit that alkoxyl replaces, alkyl and the simultaneously-substituted conjugate unit of alkoxyl；0 < x≤1,0≤y < 1, x+y=1；N is the integer of 3～1000.
Described Ar conjugate unit includes ethylene support group, acetylene support group, the aromatic rings that hydrocarbon atom is constituted, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, the aromatic heterocycle that carbon nitrogen oxygen hydrogen atom is constituted, the aromatic heterocycle that carbon sulfur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, carbon nitrogen sulfur hydrogen atom constitute aromatic heterocycle, carbon silicon sulfur hydrogen atom constitute aromatic heterocycle in one or its multiple combination.
Being carried out copolymerization with Ar monomer respectively by the phenanthridines-5-one monomers containing pyrido and prepare of the described conjugated polymer containing pyrido phenanthridines-5-ketone.
Described phenanthridines-5-the one monomers containing pyrido is 10-alkoxyl-4-alkyl-2,7-dihalopyridine phenanthridines-5 ketone (formula II c), 10-alkoxyl-4-alkyl-2, the one in 7-bis-(2-halo-thiophene-5-) pyrido phenanthridines-5 ketone (formula II d), its general structure is as follows:
Wherein, R is C1～C24Alkyl；X is the one in halogen Cl, Br or I.
The preparation method of described 10-alkoxyl-4-alkyl-2,7-two (2-halo-thiophene-5-) pyrido phenanthridines-5 ketone is:
(1) by the 10-alkoxyl-4-alkyl-2 of the above-mentioned 2mmol prepared, the 2-tin trimethyl thiophene of 7-dihalopyridine phenanthridines-5 ketone and 3.5mmol, palladium is closed as catalyst using four (triphenyl phosphorus) of 0.08mmol, in the toluene of 30mL 100 DEG C reaction 18 hours after, it is poured into water and extracts, it is then passed through silica gel chromatographic column separating-purifying and obtains 10-alkoxyl-4-alkyl-2,7-bis-thiophene pyrido phenanthridines-5 ketone.
(2) again by the 10-alkoxyl-4-alkyl-2 of the 0.7mmol of preparation in step (1), 7-bis-thiophene pyrido phenanthridines-5 ketone in the chloroform of 50mL with the NBS(N-bromosuccinimide of 1.6mmol, N-bromo-succinimide) react 12 hours after, after removing solvent, recrystallization can obtain 10-alkoxyl-4-alkyl-2,7-bis-(2-halo-thiophene-5-) pyrido phenanthridines-5 ketone.
Described Ar monomer is preferably the aromatic rings that hydrocarbon atom is constituted, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, the aromatic heterocycle that carbon nitrogen oxygen hydrogen atom is constituted, the aromatic heterocycle that carbon sulfur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, the aromatic heterocycle that carbon nitrogen sulfur hydrogen atom is constituted, one or more combinations in the aromatic heterocycle that carbon silicon sulfur hydrogen atom is constituted；
Described Ar monomer is more preferably fluorenes, carbazole, di-thiophene, dithieno [3,2-b:2', 3'-d] Silole, the double; two thiophene of benzo, di-thiofuran ethylene supports, bithiophene benzthiadiazole, two thiophene dialkoxy benzo thiadiazoles, two thiophene difluoro diazosulfides, two thiophene pyrroles pyrroledione, the double; two thiophene of dialkylthiophene benzo, dialkyl group bithiophene, bithiophene, the one in thienothiophene；
The described preparation method containing the conjugated polymer of pyrido phenanthridines-5-ketone is pyrido phenanthridines-5-one monomers and Ar monomer to be carried out copolymerization prepare, and concrete reactions steps is as follows:
Add containing pyrido phenanthridines-5-one monomers 0.25mmol in a nitrogen atmosphere in reaction bulb, Ar monomer 0.25mmol, it is dissolved in 10mL organic solvent, add 0.01mmol palladium complex catalyst, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, make eluant, concentrate eluant with toluene, settling in methanol, end product is the dry conjugated polymer obtaining pyrido phenanthridines-5-ketone under vacuo.
Described organic solvent is toluene, oxolane (THF) or at least one in chlorobenzene (CB)；
Described palladium complex catalyst is that four (triphenyl phosphorus) close palladium, three (dibenzalacetone) two palladium, or the one in two (triphenyl phosphorus) palladium chloride；
The described conjugated polymer containing pyrido phenanthridines-5-ketone can be applicable to following aspect:
(1) luminescent layer of polymer LED device is prepared.
(2) semiconductor active layer in polymer field effect transistor is prepared.
(3) active layer of polymer solar photovoltaic cell is prepared.
(4) being applied to the donor phase of polymer body heterojunction solar cell, it is with electron acceptor material C60Or derivatives thereof, organic electronic acceptor material or inorganic nano-crystal are mixed and made into solution, are coated on ito glass or cushion, prepare into thin film, and then evaporation metal prepares into device thereon.
Compared with prior art, the invention have the advantages that and effect:
Containing the conjugated polymer novel structure of pyrido phenanthridines-5-ketone, there is originality.Conjugated polymer containing pyrido phenanthridines-5-ketone has several functions, has fluorescence and high fluorescence efficiency, can apply to make the luminescent layer of polymer LED device；The planar structure having had and higher mobility, can apply to polymer field effect transistor；Sunlight being had absorbability, can apply to the active layer of polymer solar cells, relevant solar cell has high energy conversion efficiency.
Accompanying drawing explanation
Fig. 1 is the film absorption spectrogram of polymer prepared by embodiment 15.
Fig. 2 is the J-V curve chart of the device utilizing embodiment 15 resulting polymers to prepare in embodiment 20.
Detailed description of the invention
Below in conjunction with specific embodiment, the preparation and application of the conjugated polymer containing pyrido phenanthridines-5-ketone are further described.But protection domain of the presently claimed invention is not limited to the scope involved by embodiment.
Embodiment 1:
10-alkoxyl-4-alkyl-2, the preparation of 7-diiodopyridine phenanthridines-5-ketone, reaction equation is such as shown in Formula X I:
It is explained preparing 10-n-dodecane oxygen base-4-dodecyl-2,7-diiodopyridine phenanthridines-5-ketone.500mL single port flask adds 2,7-bis-iodo-5, the 10-diketone-4 prepared in 200mLDMF and embodiment 3,9-diaza pyrene (4.9g, after 10mmol), add potassium tert-butoxide (2.5g, 22mmol), after stirring 10 minutes, add 1-bromine n-dodecane (7.5g, 30mmol), after reacting 30 hours, mixed liquor is poured in 500mL water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic facies, removes solvent, obtain white solid 10-n-dodecane oxygen base-4-dodecyl-2,7-diiodopyridine phenanthridines-5-ketone (2.5g, productivity 30%) with silica gel column chromatography chromatographic column separating-purifying after separation.
It is explained preparing 10-n-tetradecane oxygen base-4-n-tetradecane base-2,7-diiodopyridine phenanthridines-5-ketone again.500mL single port flask adds 2,7-bis-iodo-5, the 10-diketone-4 prepared in 200mLDMF and embodiment 3,9-diaza pyrene (4.9g, after 10mmol), add potassium tert-butoxide (2.5g, 22mmol), after stirring 10 minutes, add 1-bromine n-tetradecane (8.3g, 30mmol), after reacting 30 hours, mixed liquor is poured in 500mL water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic facies, removes solvent, obtain white solid 10-n-tetradecane oxygen base-4-n-tetradecane base-2,7-diiodopyridine phenanthridines-5-ketone (2.8g, productivity 32%) with silicon silica gel column chromatography chromatographic column separating-purifying after separation
Pungent to prepare 10-(2-butyl again) oxygen base-4-(2-butyl is pungent) base-2,7-diiodopyridine phenanthridines-5-ketone is explained.500mL single port flask adds 2,7-bis-iodo-5, the 10-diketone-4 prepared in 200mLDMF and embodiment 3,9-diaza pyrene (4.9g, after 10mmol), add potassium tert-butoxide (2.5g, 22mmol), after stirring 10 minutes, add 1-bromo-2-butyl octane (7.5g, 30mmol), after reacting 30 hours, mixed liquor is poured in 500mL water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic facies, removes solvent, obtain white solid 10-(2-butyl with silica gel column chromatography chromatographic column separating-purifying pungent after separation) oxygen base-4-(2-butyl is pungent) base-2,7-diiodopyridine phenanthridines-5-ketone (3.0g, productivity 31%).
Again to prepare 10-(2-hexyl decane) oxygen base-4-(2-hexyl decane) base-2,7-diiodopyridine phenanthridines-5-ketone is explained.500mL single port flask adds 2,7-bis-iodo-5, the 10-diketone-4 prepared in 200mLDMF and embodiment 3,9-diaza pyrene (4.9g, after 10mmol), add potassium tert-butoxide (2.5g, 22mmol), after stirring 10 minutes, add 1-bromine 2-hexyl decane (9.1g, 30mmol), after reacting 30 hours, mixed liquor is poured in 500mL water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic facies, removes solvent, obtain white solid 10-(2-hexyl decane with silica gel column chromatography chromatographic column separating-purifying after separation) oxygen base-4-(2-hexyl decane) base-2,7-diiodopyridine phenanthridines-5-ketone (3.4g, productivity 37%).
Again to prepare 10-(2-octyldodecyl) oxygen base-4-(2-octyldodecyl) base-2,7-diiodopyridine phenanthridines-5-ketone is explained.500mL single port flask adds 2,7-bis-iodo-5, the 10-diketone-4 prepared in 200mLDMF and embodiment 3,9-diaza pyrene (4.9g, after 10mmol), add potassium tert-butoxide (2.5g, 22mmol), after stirring 10 minutes, add the bromo-2-octyldodecyl (10.8g, 30mmol) of 1-, after reacting 30 hours, mixed liquor is poured in 500mL water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic facies, removes solvent, obtain white solid 10-(2-octyldodecyl with silica gel column chromatography chromatographic column separating-purifying after separation) oxygen base-4-(2-octyldodecyl) base-2,7-diiodopyridine phenanthridines-5-ketone (4.1g, 40%).
Again to prepare 10-(2-decyl myristyl) oxygen base-4-(2-decyl myristyl) base-2,7-diiodopyridine phenanthridines-5-ketone is explained.500mL single port flask adds 2,7-bis-iodo-5, the 10-diketone-4 prepared in 200mLDMF and embodiment 3,9-diaza pyrene (4.9g, after 10mmol), add potassium tert-butoxide (2.5g, 22mmol), after stirring 10 minutes, add the 1-bromo-2-decyl tetradecane (12.5g, 30mmol), after reacting 30 hours, mixed liquor is poured in 500mL water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic facies, solvent is removed after separation, white solid 10-(2-decyl myristyl is obtained with silica gel column chromatography chromatographic column separating-purifying) oxygen base-4-(2-decyl myristyl) base-2,7-diiodopyridine phenanthridines-5-ketone (4.0g, productivity 37%).
10-alkoxyl-4-alkyl-2,7-diiodopyridine phenanthridines-5-ketone group are not limited only to this.
Embodiment 2:
10-alkoxyl-4-alkyl-2, the preparation of 7-bis-thiophene pyrido phenanthridines-5-ketone, reaction equation is such as shown in Formula X II:
It is explained preparing 10-n-dodecane oxygen base-4-dodecyl-2,7-two thiophene pyrido phenanthridines-5-ketone.Under argon shield; 50mL there-necked flask adds the 10-n-dodecane oxygen base-4-dodecyl-2 prepared in embodiment 21; 7-diiodopyridine phenanthridines-5-ketone (1.65g; 2mmol); 2-tributyl tin thiophene (1.61g, 3.5mmol), and 30mL toluene; four (triphenyl phosphorus) closes (90mg, 0.08mmol).Heat to 100 degrees Celsius of reactions 18 hours.Reaction mixture is poured in 200mL water, and use dichloromethane extraction product.Anhydrous magnesium sulfate dries organic facies, removes solvent, obtain yellow solid 10-n-dodecane oxygen base-4-dodecyl-2,7-bis-thiophene pyrido phenanthridines-5-ketone (1.42g, productivity 91%) with silica gel chromatographic column separating-purifying after separation.
10-alkoxyl-4-alkyl-2, the alkyl in 7-bis-thiophene pyrido phenanthridines-5-ketone also includes: n-tetradecane base, 2-butyl octyl, 2-hexyl decyl, 2-octyldodecyl and 2-decyl myristyl, but is not limited only to this.
Embodiment 3:
10-alkoxyl-4-alkyl-2, the preparation of 7-bis-(2-bromo-thiophene-5-) pyrido phenanthridines-5-ketone, reaction equation is Formula X III such as:
It is explained preparing 10-n-dodecane oxygen base-4-dodecyl-2,7-two (2-bromo-thiophene-5-) pyrido phenanthridines-5-ketone.
In 250 milliliters of single port flasks, adding 10-n-dodecane oxygen base-4-dodecyl-2 prepared in embodiment 22,7-bis-thiophene pyrido phenanthridines-5-ketone (0.52g, 0.7mmol) and 50mL chloroform stir.NBS(N-bromosuccinimide, N-bromo-succinimide is added under condition of ice bath) (0.28g, 1.6mmol), react 12 hours.After being removed by solvent, solid is recrystallization in chloroform, obtains yellow solid 10-n-dodecane oxygen base-4-dodecyl-2,7-bis-(2-bromo-thiophene-5-) pyrido phenanthridines-5-ketone (0.50g, 79%).
10-alkoxyl-4-alkyl-2, the alkyl in 7-bis-(2-bromo-thiophene-5-) pyrido phenanthridines-5-ketone also includes: n-tetradecane base, 2-butyl octyl, 2-hexyl decyl, 2-octyldodecyl and 2-decyl myristyl, but is not limited only to this.
Embodiment 4:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and fluorenes, reaction equation is such as shown in Formula X IVa:
The 10-n-dodecane oxygen base-4-dodecyl-2 prepared in embodiment 21 is added in a nitrogen atmosphere in reaction bulb, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 9, 9-di-n-octyl-2, 7-bis-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-base) fluorenes 0.25mmol, it is dissolved in 10 milliliters of toluene, add the tetraethyl ammonium hydroxide aqueous solution that 2mL weight concentration is 25%, 10mg tetra-(triphenyl phosphorus) closes palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is the dry conjugated polymer obtaining yellow pyridine phenanthridines-5-ketone and fluorenes under vacuo.The number-average molecular weight of this polymer is 14000, and weight average molecular weight is 29000.
Embodiment 5:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and carbazole, reaction equation is such as shown in Formula X IVb:
The 10-n-dodecane oxygen base-4-dodecyl-2 prepared in embodiment 21 is added in a nitrogen atmosphere in reaction bulb, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, N-octyl group nonyl-2, 7-bis-(4, 4, 5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-base) carbazole 0.25mmol, it is dissolved in 10mL toluene, add the tetraethyl ammonium hydroxide aqueous solution that 2mL weight concentration is 25%, 10mg tetra-(triphenyl phosphorus) closes palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is the dry conjugated polymer obtaining yellow pyrido phenanthridines-5-ketone and carbazole under vacuo.The number-average molecular weight of this polymer is 11000, and weight average molecular weight is 22000.
Embodiment 6:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and di-thiophene, reaction equation is such as shown in Formula X IVc:
The 10-(2-butyl prepared is added in embodiment 21 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 5, 5 '-two tin trimethyls-(2, 2 '-di-thiophene) 0.25mmol, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is the dry conjugated polymer obtaining orange pyrido phenanthridines-5-ketone and di-thiophene under vacuo.The number-average molecular weight of this polymer is 21000, and weight average molecular weight is 39000.
Embodiment 7:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and dithieno [3,2-b:2', 3'-d] Silole, reaction equation is such as shown in Formula X IVd:
The 10-n-dodecane oxygen base-4-dodecyl-2 prepared in embodiment 21 is added in a nitrogen atmosphere in reaction bulb, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 4, 4 '-two (ethyl) hexyl-5, 5 '-two tin trimethyls-dithieno [3, 2-b:2', 3'-d] Silole 0.25mmol, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains red pyrido phenanthridines-5-ketone and dithieno [3, 2-b:2', 3'-d] conjugated polymer of Silole.The number-average molecular weight of this polymer is 20000, and weight average molecular weight is 37000.
Embodiment 8:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and the double; two thiophene of benzo, reaction equation is such as shown in Formula X IVe:
The 10-(2-butyl prepared is added in embodiment 21 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 4, 8-bis-n-dodecane oxygen base-2, the double, two thiophene 0.25mmol of 6-bis-tin trimethyl benzo, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is the dry conjugated polymer obtaining red pyrido phenanthridines-5-ketone and the double, two thiophene of benzo under vacuo.The number-average molecular weight of this polymer is 21000, and weight average molecular weight is 39000.
Embodiment 9:
The preparation of the conjugated polymer that pyrido phenanthridines-5-ketone supports with di-thiofuran ethylene, reaction equation is such as shown in Formula X IVf:
The 10-(2-hexyl decane prepared in embodiment 21 is added in a nitrogen atmosphere in reaction bulb) oxygen base-4-(2-hexyl decane) base-2, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 1, 2-bis-(5-tin trimethyl thiophene-2-) vinylene 0.25mmol, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, the conjugated polymer of the end product dry pyrido phenanthridines-5-ketone obtaining redness and di-thiofuran ethylene support under vacuo.The number-average molecular weight of this polymer is 23000, and weight average molecular weight is 44000.
Embodiment 10:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and bithiophene benzthiadiazole, reaction equation is such as shown in Formula X IVg:
The 10-(2-decyl tetradecane prepared in embodiment 21 is added in a nitrogen atmosphere in reaction bulb) the oxygen base-4-(2-decyl tetradecane) base-2, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 4, 7-bis-(5-tin trimethyl thiophene-2-) benzo [2, 1, 3] thiadiazoles 0.25mmol, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the pyrido phenanthridines-5-ketone of black and the conjugated polymer of bithiophene benzthiadiazole.The number-average molecular weight of this polymer is 18000, and weight average molecular weight is 33000.
Embodiment 11:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and two thiophene dialkoxy benzo thiadiazoles, reaction equation is such as shown in Formula X IVh:
The 10-(2-butyl prepared is added in embodiment 21 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 4, 7-bis-(5-tin trimethyl thiophene-2-) 5, 6-bis-n-dodecane oxygen base benzo [2, 1, 3] thiadiazoles 0.25mmol, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the pyrido phenanthridines-5-ketone of black and the conjugated polymer of two thiophene dialkoxy benzo thiadiazoles.The number-average molecular weight of this polymer is 14000, and weight average molecular weight is 33000.
Embodiment 12:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and two thiophene difluoro diazosulfides, reaction equation is such as shown in Formula X IVi:
The 10-(2-decyl myristyl prepared in embodiment 21 is added in a nitrogen atmosphere in reaction bulb) oxygen base-4-(2-decyl myristyl) base-2, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 4, 7-bis-(5-tin trimethyl thiophene-2-) 5, 6-difluoro benzo [2, 1, 3] thiadiazoles 0.25mmol, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the pyrido phenanthridines-5-ketone of black and the conjugated polymer of two thiophene difluoro diazosulfides.The number-average molecular weight of this polymer is 15000, and weight average molecular weight is 31000.
Embodiment 13:
The preparation of the conjugated polymer of pyrido phenanthridines-5-ketone and two thiophene pyrroles pyrroledione, reaction equation is such as shown in Formula X IVj:
The 10-(2-butyl prepared is added in embodiment 21 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-diiodopyridine phenanthridines-5-ketone 0.25mmol, 2, 5-bis-(ethylhexyl)-3, 6-bis-(5-tin trimethyl thiophene-2-) pyrrolo-pyrrole-dione 0.25mmol, it is dissolved in 10mL toluene, add 10mg tetra-(triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the pyrido phenanthridines-5-ketone of black and the conjugated polymer of two thiophene pyrroles pyrroledione.The number-average molecular weight of this polymer is 13000, and weight average molecular weight is 27000.
Embodiment 14:
The preparation of the conjugated polymer of 2,7-bis-thiophene pyrido phenanthridines-5-ketone and dithieno [3,2-b:2', 3'-d] Silole, reaction equation is such as shown in Formula X Va:
The 10-(2-butyl prepared is added in embodiment 23 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-bis-(2-bromothiophene-5-) pyrido phenanthridines-5-ketone 0.25mmol, 4, 4 '-two (ethyl) hexyl-5, 5 '-two tin trimethyls-dithieno [3, 2-b:2', 3'-d] Silole 0.25mmol, it is dissolved in 10 milliliters of toluene, add 10 milligram four (triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the 2 of black, 7-bis-thiophene pyrido phenanthridines-5-ketone and dithieno [3, 2-b:2', 3'-d] conjugated polymer of Silole.The number-average molecular weight of this polymer is 14000, and weight average molecular weight is 30000.
Embodiment 15:
The preparation of the conjugated polymer of 2,7-bis-thiophene pyrido phenanthridines-5-ketone and the double; two thiophene of benzo, reaction equation is such as shown in Formula X Vb:
The 10-(2-butyl prepared is added in embodiment 23 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-bis-(2-bromothiophene-5-) pyrido phenanthridines-5-ketone 0.25mmol, 4, 8-bis-n-dodecane oxygen base-2, the double, two thiophene 0.25mmol of 6-bis-tin trimethyls-benzo, it is dissolved in 10 milliliters of toluene, add 10 milligram four (triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the 2 of reddish black, the conjugated polymer of 7-bis-thiophene pyrido phenanthridines-5-ketone and the double, two thiophene of benzo.The number-average molecular weight of this polymer is 11000, and weight average molecular weight is 25000.The film absorption spectrum of this polymer presents peak value (such as Fig. 1) at 514nm place.
Embodiment 16:
The preparation of the conjugated polymer of 2,7-bis-thiophene pyrido phenanthridines-5-ketone and the double; two thiophene of dialkylthiophene benzo, reaction equation is such as shown in Formula X Vc:
The 10-(2-butyl prepared is added in embodiment 23 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-bis-(2-bromothiophene-5-) pyrido phenanthridines-5-ketone 0.25mmol, 4, 8-bis-(4, 5-dioctyl thiophene-2-) 2, the double, two thiophene 0.25mmol of 6-bis-tin trimethyl benzo, it is dissolved in 10 milliliters of toluene, add 10 milligram four (triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the 2 of redness, the conjugated polymer of 7-bis-thiophene pyrido phenanthridines-5-ketone and the double, two thiophene of dialkylthiophene benzo.The number-average molecular weight of this polymer is 16000, and weight average molecular weight is 31000.
Embodiment 17:
The preparation of the conjugated polymer of 2,7-bis-thiophene pyrido phenanthridines-5-ketone and dialkyl group bithiophene, reaction equation is such as shown in Formula X Vd:
The 10-(2-butyl prepared is added in embodiment 23 in a nitrogen atmosphere pungent in reaction bulb) oxygen base-4-(2-butyl is pungent) base-2, 7-bis-(2-bromothiophene-5-) pyrido phenanthridines-5-ketone 0.25mmol, 4, 4 '-two dodecyls-5, 5 '-two tin trimethyls-2, 2 '-bithiophene 0.25mmol, it is dissolved in 10 milliliters of toluene, add 10 milligram four (triphenyl phosphorus) and close palladium, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography, eluant is made with toluene, concentrate eluant, methanol settles, end product is dry under vacuo obtains the 2 of redness, the conjugated polymer of 7-bis-thiophene pyrido phenanthridines-5-ketone and dialkyl group bithiophene.The number-average molecular weight of this polymer is 15000, and weight average molecular weight is 31000.
Embodiment 18:
The preparation of polymer LED device
Ito glass, after ultrasonic waves for cleaning, processes with oxygen-Plasma, and the square resistance of ito glass is 10 Ω/cm2.Hole injection layer polymer is PEDOT or PVK, and luminescent layer adopts the one of which of synthesized polymer in above example.Hole injection layer and polymer light-emitting layer all adopt the mode of spin coating to make.Cathode electrode is respectively adopted Ca/Al or Ba/Al metal.
Ito glass noted earlier refers to indium tin oxide-coated glass；PEDOT refers to gather (3,4-ethylenedioxythiophene)；PVK refers to Polyvinyl carbazole.Wherein, ito glass buys gained from Shenzhen Nan Bo group company limited, and PEDOT and PVK all buys gained from Sigma-Aldrich company.
Embodiment 19:
The preparation of polymer field effect transistor device
Ito glass, after ultrasonic waves for cleaning, processes with oxygen-Plasma, and the square resistance of ito glass is 10 Ω/cm2.Use magnetron sputtering deposition SiO2Insulating barrier, is spun on insulating barrier by the one of which of polymer synthesized in above example, and source/drain electrode is Au or Ag.
Embodiment 20:
The preparation of polymer solar cells device and performance
Ito glass, after ultrasonic waves for cleaning, processes with oxygen-Plasma, and the square resistance of ito glass is 10 Ω/cm2.Spin coating PEDOT on ito glass, is configured to after solution with PCBM to mix, be spin-coated on PEDT layer and form active layer respectively by the one of which of polymer synthesized in above example.Finally steam upper Al metal electrode.Its battery behavior is measured under the irradiation of the AM1.5 simulated solar irradiation of 100 milliwatt every square centimeter.
Polymer prepared by embodiment 15 and PCBM dichloro-benzenes are solvent, by the active layer that polymer and PCBM weight ratio are 1:1 mixing spin on polymers solar cell, the open-circuit voltage of gained battery device 0.66 volt, short circuit current 1.51 milliamperes every square centimeter, fill factor, curve factor 46.7%, energy conversion efficiency 0.46%.Corresponding device J-V curve is shown in Fig. 2.
Described PCBM is the abbreviation of English " methanofullerene [6,6]-phenylC61-butyricacidmethylester ".
Above-described embodiment is the present invention preferably embodiment; but embodiments of the present invention are also not restricted to the described embodiments; the change made under other any spirit without departing from the present invention and principle, modification, replacement, combination, simplification; all should be the substitute mode of equivalence, be included within protection scope of the present invention.

Claims (9)

1. containing the conjugated polymer of pyrido phenanthridines-5-ketone, it is characterised in that: there is the structure shown in following formula I c or formula I d:
Wherein, R is C1～C24Alkyl；Ar is the one in following conjugate unit: the conjugate unit of alkyl replacement, the conjugate unit that alkoxyl replaces, alkyl and the simultaneously-substituted conjugate unit of alkoxyl；Or Ar is one or more combinations in following conjugate unit: ethylene support group, acetylene support group, the aromatic rings that hydrocarbon atom is constituted, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, the aromatic heterocycle that carbon nitrogen oxygen hydrogen atom is constituted, the aromatic heterocycle that carbon sulfur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, the aromatic heterocycle that carbon nitrogen sulfur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon sulfur hydrogen atom is constituted；0 < x≤1,0≤y < 1, x+y=1；N is the integer of 3～1000.
2. the method for the preparation conjugated polymer containing pyrido phenanthridines-5-ketone described in claim 1, it is characterised in that carried out copolymerization by the monomer containing pyrido phenanthridines-5-ketone and Ar monomer and prepare.
3. preparation according to claim 2 is containing the method for the conjugated polymer of pyrido phenanthridines-5-ketone, it is characterized in that: the described phenanthridines-5-one monomers containing pyrido is 10-alkoxyl-4-alkyl-2,7-dihalopyridine phenanthridines-5-ketone (formula II c), 10-alkoxyl-4-alkyl-2, one in 7-bis-(2-halo-thiophene-5-) pyrido phenanthridines-5-ketone (formula II d), its general structure is as follows:
Wherein, R is C1～C24Alkyl；X is the one in halogen Cl, Br or I.
4. preparation according to claim 3 is containing the method for the conjugated polymer of pyrido phenanthridines-5-ketone, it is characterised in that: described 10-alkoxyl-4-alkyl-2, the preparation method of 7-dihalopyridine phenanthridines-5-ketone is:
By the 2 of 10mmol, 7-dihalo-5,10-diketone-4,9-diaza pyrene is at the N of 200mL, after dinethylformamide reacts 30 hours with the 1-bromoalkane of the potassium tert-butoxide of 22mmol and 30mmol, it is poured into water and extracts, be then passed through silica gel chromatographic column separating-purifying and obtain rearrangement product 10-alkoxyl-4-alkyl-2,7-dihalopyridine phenanthridines-5-ketone.
5. preparation according to claim 3 is containing the method for the conjugated polymer of pyrido phenanthridines-5-ketone, it is characterised in that: described 10-alkoxyl-4-alkyl-2, the preparation method of 7-bis-(2-halo-thiophene-5-) pyrido phenanthridines-5-ketone is:
(1) by the 10-alkoxyl-4-alkyl-2 of 2mmol, the 2-tin trimethyl thiophene of 7-dihalopyridine phenanthridines-5-ketone and 3.5mmol, palladium is closed as catalyst using four (triphenyl phosphorus) of 0.08mmol, in the toluene of 30mL 100 DEG C reaction 18 hours after, it is poured into water and extracts, it is then passed through silica gel chromatographic column separating-purifying and obtains 10-alkoxyl-4-alkyl-2,7-bis-thiophene pyrido phenanthridines-5-ketone；
(2) again by the 10-alkoxyl-4-alkyl-2 of the 0.7mmol of preparation in step (1), after 7-bis-thiophene pyrido phenanthridines-5-ketone reacts 12 hours with the N-bromo-succinimide of 1.6mmol in the chloroform of 50mL, after removing solvent, namely recrystallization obtains 10-alkoxyl-4-alkyl-2,7-bis-(2-halo-thiophene-5-) pyrido phenanthridines-5-ketone.
6. preparation according to claim 3 is containing the method for the conjugated polymer of pyrido phenanthridines-5-ketone, it is characterized in that: described Ar monomer is the aromatic rings that hydrocarbon atom is constituted, the aromatic heterocycle that carbon nitrogen hydrogen atom is constituted, the aromatic heterocycle that carbon nitrogen oxygen hydrogen atom is constituted, the aromatic heterocycle that carbon sulfur hydrogen atom is constituted, the aromatic heterocycle that carbon silicon hydrogen atom is constituted, the aromatic heterocycle that carbon nitrogen sulfur hydrogen atom is constituted, one or more combinations in the aromatic heterocycle that carbon silicon sulfur hydrogen atom is constituted.
7. preparation according to claim 3 is containing the method for the conjugated polymer of pyrido phenanthridines-5-ketone, it is characterised in that specifically comprise the following steps that
Add containing pyrido phenanthridines-5-one monomers 0.25mmol in a nitrogen atmosphere in reaction bulb, with Ar monomer 0.25mmol, add 10mL organic solvent dissolution, add 0.01mmol palladium complex catalyst, it is heated to reflux lower stirring reaction 48 hours, after cooling, polymer is settled out with methanol, dried product is dissolved in toluene, adopt silica gel column chromatography chromatographic column, make eluant, concentrate eluant with toluene, settling in methanol, end product is the dry conjugated polymer obtained containing pyrido phenanthridines-5-one monomers under vacuo；
Described organic solvent is toluene, oxolane (THF) or at least one in chlorobenzene (CB)；
Described palladium complex catalyst is that four (triphenyl phosphorus) close palladium, three (dibenzalacetone) two palladium, or the one in two (triphenyl phosphorus) palladium chloride.
8. the semiconductor active layer in preparing the luminescent layer of polymer LED device, preparation polymer field effect transistor of the conjugated polymer containing pyrido phenanthridines-5-ketone described in claim 1 or the application in preparing the active layer of polymer solar photovoltaic cell.
9. the application of the conjugated polymer containing pyrido phenanthridines-5-ketone described in claim 1, is characterized in that being applied to the donor phase of polymer body heterojunction solar cell, with electron acceptor material C60Or derivatives thereof, organic electronic acceptor material or inorganic nano-crystal are mixed and made into solution, are coated on ito glass or cushion, prepare into thin film, and then evaporation metal prepares into device thereon.
CN201310217355.1A 2013-06-03 2013-06-03 Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application Expired - Fee Related CN103319694B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201310217355.1A CN103319694B (en) 2013-06-03 2013-06-03 Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201310217355.1A CN103319694B (en) 2013-06-03 2013-06-03 Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application

Publications (2)

Publication Number Publication Date
CN103319694A CN103319694A (en) 2013-09-25
CN103319694B true CN103319694B (en) 2016-06-29

Family

ID=49188773

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201310217355.1A Expired - Fee Related CN103319694B (en) 2013-06-03 2013-06-03 Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application

Country Status (1)

Country Link
CN (1) CN103319694B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104725612B (en) * 2015-03-24 2016-09-21 中国科学院化学研究所 Conjugated polymer material of one class side chain hydrogen bonds group and preparation method and application
CN105860032B (en) * 2016-02-29 2019-05-14 华南理工大学 A kind of organic semiconducting materials and the preparation method and application thereof of -6- of dialkyl group containing 2,9- alkoxy phenanthridines unit

Also Published As

Publication number Publication date
CN103319694A (en) 2013-09-25

Similar Documents

Publication Publication Date Title
CN102725331B (en) Cyclopentadienedithiophene-quinoxaline conjugated polymer and preparation method and uses thereof
EP2615095B1 (en) Benzodithiophene organic semiconductive material, preparation method and use thereof
EP2573125A1 (en) Conjugated polymer containing dithienopyrrole-quinoxaline, preparation method and uses thereof
CN102858841B (en) Quinoxaline conjugated polymer containing fused-ring thiophehe unit, preparation method and uses thereof
EP2927258B1 (en) Benzodithiophene based copolymer containing thieno [3,4-b]thiophene units and preparing method and applications thereof
EP2586810A1 (en) Conjugated polymer based on benzodithiophene and thienopyrazine, preparation method and uses thereof
CN103059271B (en) Conjugated polymer containing 5,10-diketone-4,9-diazapyrene and preparation thereof
EP2581399B1 (en) Conjugated polymer based on perylene tetracarboxylic acid diimide and benzodithiophene and its preparation method and application
CN103319695B (en) Conjugated polymer containing 4,9-diaza pyrene and preparation method thereof and application
EP2530084B1 (en) Copolymer containing fluorenylporphyrin-anthracene, preparation method and use thereof
CN101885834B (en) Conjugated polymer containing 4,5-ethylene-2,7-carbazole as well as preparation method and application thereof
EP2927259B1 (en) Benzodithiophene based copolymer containing thiophene pyrroledione units and preparing method and applications thereof
CN102206329B (en) Dithiophene silole-quinoxalines conjugated polymer, and its preparation method and application
CN104119504A (en) Conjugated polymer material containing pyrrole indolodithiapentalene-dithieno benzothiadiazole and preparation method and application thereof
CN103319694B (en) Conjugated polymer containing pyrido phenanthridines-5-ketone and preparation method thereof and application
EP2657226B1 (en) Organic semiconductor material, preparation methods and uses thereof
CN102344553B (en) Naphthalenetetracarboxylic acid diimide organic semiconductor material, preparation process thereof and application thereof
EP2617754A1 (en) Fluorene containing organic semiconductor material, preparation method and use thereof
CN104045812B (en) A kind of containing thioxothiazole-dithieno pyrroles-benzo two thiophene copolymers and preparation method and application
CN102477143B (en) Fluorene-containing organic semiconductor material, and preparation method and application thereof
CN102206330B (en) Bi-thiophene silole-containing conjugated polymer and preparation method and application thereof
CN102234366B (en) Thiophene-containing perylene tetracarboxylic diimide copolymer, and preparation method and application thereof
CN102344551B (en) Organic semiconductor material containing naphthalene tetracarboxylic acid diimide, preparation method and application thereof
CN103848968B (en) A kind of containing Thienopyrroles diketone-dibenzothiophene benzo two thiophen polymer and preparation and application thereof
JP2016507594A (en) Benzodithiophene-based copolymer containing isoindoline-1,3-diketone unit, production method, and method of use thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160629