CN104250365A - Anthraquinonyl group-containing polymer, preparation method thereof, and organic solar cell device - Google Patents

Anthraquinonyl group-containing polymer, preparation method thereof, and organic solar cell device Download PDF

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CN104250365A
CN104250365A CN201310259890.3A CN201310259890A CN104250365A CN 104250365 A CN104250365 A CN 104250365A CN 201310259890 A CN201310259890 A CN 201310259890A CN 104250365 A CN104250365 A CN 104250365A
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anthraquinonyl
polymkeric substance
preparation
substance containing
bis
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周明杰
张振华
王平
张娟娟
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

The invention belongs to the field of organic semiconductors, and discloses an anthraquinonyl group-containing polymer, a preparation method thereof, and an organic solar cell device. The structural general formula of the above main body material is shown in the specification. In the formula, R1 and R2 respectively represent C1-C20 alkyl groups, and n is an integer from 13 to 97. In the anthraquinonyl group-containing polymer, anthraquinone is an electron transfer unit, and is in favor of transferring charges; and benzodithiophene is an important solar cell material and has an excellent photoelectric performance, a phenyl ring can be modified with other groups to improve the dissolving performance and the film forming performance of copolymerized benzodithiophene, and dibenzothiophene is introduced to the main chain of the anthraquinonyl group-containing polymer to realize the carrier balance of the solar cell device in order to solve the low efficiency problem of the organic solar cell device.

Description

A kind of polymkeric substance containing anthraquinonyl and preparation method thereof and organic solar batteries device
Technical field
The present invention relates to organic semiconductor material field, particularly relate to a kind of polymkeric substance containing anthraquinonyl and preparation method thereof.The invention still further relates to a kind of this polymkeric substance containing anthraquinonyl that uses as the organic solar batteries device of active layer electron donor material.
Background technology
Utilize cheap material prepares low cost, dynamical solar cell is photovoltaic art always study hotspot and difficult point.The advantages such as organic semiconductor material is easy to get with its raw material, cheap, technique is simple, stability is strong, photovoltaic effect is good receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE(N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C 60between Photo-induced electron transfer phenomenon after, organic polymer solar cell becomes the focus of research gradually.The research of this respect in recent years achieves development at full speed, but organic polymer solar cell is still much lower than the efficiency of conversion of inorganic solar cell.In order to make organic polymer solar cell be on the actual application, develop the top priority that the type material with higher-energy efficiency of conversion is still this field.
Summary of the invention
Based on the problems referred to above, problem to be solved by this invention is the polymkeric substance containing anthraquinonyl providing a kind of transformation efficiency high.
Technical scheme of the present invention is as follows:
A kind of polymkeric substance containing anthraquinonyl provided by the invention, its general structure is as follows:
In formula, R 1, R 2be C 1~ C 20alkyl, n is the integer of 13-97
Another object of the embodiment of the present invention is the preparation method providing a kind of polymkeric substance containing anthraquinonyl, comprises the steps:
The compd A providing following structural formula to represent respectively and B,
A: i.e. 2,6-bis-tin trimethyl-4,8-bis-(5-alkylthrophene) benzene 1,4-Dithiapentalenes;
B: i.e. 2,6-bis-bromo-1,5-bis-(alkoxyl group) anthracene-9,10-diketone;
Under oxygen-free environment (oxygen-free environment of at least one gas composition in preferred argon gas, nitrogen), be after dissolving during the compd A of 1:1 ~ 1.2 and B are added into containing catalyzer organic solvent by mol ratio, Stille coupling reaction is carried out 6 ~ 60 hours under 70 ~ 130 ° of C, polyreaction is stopped after cooling, through separating-purifying reaction solution, obtain the described polymkeric substance containing anthraquinonyl of following general structure:
In formula, R 1, R 2be C 1~ C 20alkyl, n is the integer of 13-97.
Wherein, described catalyzer is described catalyzer is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium; Or
Palladium and the tri-o-tolyl phosphine mixture of described catalyzer to be mol ratio be 1:4 ~ 8, or mol ratio is three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 of 1:4 ~ 8 ', 6 '-dimethoxy-biphenyl mixture;
The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
In a preferred embodiment, organic solvent is selected from solvent is at least one in toluene, DMF, tetrahydrofuran (THF).
In a preferred embodiment, Stille coupling reaction is at 90 ~ 120 DEG C, reacts 12 ~ 48 hours.
In a preferred embodiment, separating-purifying reaction solution comprises step:
Methyl alcohol precipitating is added in reaction solution, methyl alcohol and normal hexane extracting is used successively after being filtered by apparatus,Soxhlet's, then be that solvent extraction is to colourless with chloroform, collect chloroformic solution and be spin-dried for and obtain powder, powder after collection under vacuo after the dry 24h of 50 ° of C, obtains the described polymkeric substance containing anthraquinonyl again.
The present invention also provides a kind of organic solar batteries device, and the electron donor material of its active layer adopts the polymkeric substance containing anthraquinonyl of following structural formula:
In formula, R 1, R 2be C 1~ C 20alkyl, n is the integer of 13-97.
Of the present invention containing in the polymkeric substance of anthraquinonyl, anthraquinone is an electric transmission unit, is conducive to transferring charge; Benzene 1,4-Dithiapentalene is the important solar cell material of a class, it has excellent photoelectric properties, phenyl ring can use other base group modification, thus improve solubility property and the film forming properties of copolymerization benzene 1,4-Dithiapentalene, anthraquinonyl main polymer chain introduces dibenzothiophene, realize the carrier balance of solar cell device, thus solve organic solar batteries device low efficiency problem.Simultaneously, this polymkeric substance belongs in D-A type polymer solar battery material, larger electrophilic anthraquinonyl is an important electron acceptor(EA) unit, has band gap narrower and have the advantage such as higher uptake factor and wider absorption region to sunlight by alkoxyl group after being modified; There is band gap narrower and have higher uptake factor to sunlight and in advantages such as the wider absorption regions of 300nm ~ 700nm, these advantages can improve its light conversion efficiency greatly.
The preparation method of the above-mentioned polymkeric substance containing anthraquinonyl, has used better simply synthetic route, thus reduces technical process, and starting material are cheap and easy to get, and manufacturing cost is reduced; And the polymeric material constructions be worth is novel, solubility property is good, and film forming properties is excellent, and absorption region is wide, and effciency of energy transfer is improved.
Accompanying drawing explanation
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of the polymkeric substance containing anthraquinonyl that embodiment 1 obtains;
Fig. 2 is the structural representation of the organic solar batteries device that embodiment 6 obtains.
Embodiment
In order to understand the content of patent of the present invention better, technology case of the present invention is further illustrated below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein compd A, compd B commercially obtain.
Embodiment 1:
The polymkeric substance containing anthraquinonyl of the present embodiment, i.e. poly-{ 2,6-bis-base-4,8-bis-(5-octane base thiophene) benzene 1,4-Dithiapentalene-co-2,6-bis-base-1,5-bis-(n-octyloxy) anthracene-9,10-diketone } (representing with P1), (wherein, R1 is octane base, R2 is octane base, n=35), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under argon shield, by 2,6-bis-tin trimethyl-4,8-bis-(5-octane base thiophene) benzene 1,4-Dithiapentalene (181mg, 0.2mmol), 2,6-bis-bromo-1,5-bis-(n-octyloxy) anthracene-9,10-diketone (124mg, 0.2mmol) add in the flask filling 10ml toluene solvant, vacuumize deoxygenation and be filled with argon gas, then adding bis-triphenylphosphipalladium palladium dichloride (5.6mg, 0.008mmol); Flask is heated to 100 DEG C and carries out Stille coupling reaction 36h.Subsequently, after cooling, stop polyreaction, drip in flask in 50ml methyl alcohol and carry out sedimentation; Methyl alcohol and normal hexane extracting 24h is used successively after being filtered by apparatus,Soxhlet's.Then be that solvent extraction is extremely colourless with chloroform, collect chloroformic solution and be spin-dried for obtain red powder, after collection, 50 DEG C of dry 24h obtain P1 product under vacuo, productive rate 78%.
Test result is: Molecular weight (GPC, THF, R.I): M n=44.6kDa, M w/ M n=2.3.
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of the polymkeric substance containing anthraquinonyl that embodiment 1 obtains; As shown in Figure 1, this polymkeric substance has comparatively large wider absorption between 300nm ~ 700nm, and wherein maximum absorption band is positioned at about 558nm.
Embodiment 2:
The polymkeric substance containing anthraquinonyl of the present embodiment, i.e. poly-{ 2,6-bis-base-4,8-bis-(5-thiotolene) benzene 1,4-Dithiapentalene-co-2,6-bis-base-1,5-bis-(NSC 62789 oxygen base) anthracene-9,10-diketone } (representing with P2), (wherein, R 1for methyl, R 2for NSC 62789 base, n=62), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and argon gas gas mixture are protected, by 2, 6-bis-tin trimethyl-4, 8-bis-(5-thiotolene) benzene 1,4-Dithiapentalene (212mg, 0.3mmol), 2, 6-bis-bromo-1, 5-bis-(NSC 62789 oxygen base) anthracene-9, 10-diketone (287mg, 0.3mmol) add in the two-mouth bottle of 50mL specification with 15mL tetrahydrofuran (THF), after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min, then by tetra-triphenylphosphine palladium (4mg, 0.003mmol) add wherein, after the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 70 DEG C and carry out Stille coupling reaction 60h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, obtain P2 product after 50 DEG C of dry 24h under vacuo.Productive rate is 81%.
Test result is: Molecular weight (GPC, THF, R.I): M n=58.4kDa, M w/ M n=2.2.
Embodiment 3:
The polymkeric substance containing anthraquinonyl of the present embodiment, i.e. poly-{ 2,6-bis-base-4,8-bis-(5-NSC 62789 base thiophene) benzene 1,4-Dithiapentalene-co-2,6-bis-base-1,5-bis-(methoxyl group) anthracene-9,10-diketone } (representing with P3), (wherein, R 1for NSC 62789 base, R 2for methyl, n=13), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 2,6-bis-tin trimethyl-4,8-bis-(5-NSC 62789 base thiophene) benzene 1,4-Dithiapentalene (372mg, 0.3mmol), 2,6-bis-bromo-1,5-bis-(NSC 62789 oxygen base) anthracene-9,10-diketone (141mg, 0.33mmol), palladium (3.5mg, 0.015mmol) and three (o-methoxyphenyl) phosphine (21mg, 0.06mmol) joins the N filling 12mL, in the flask of dinethylformamide, after in flask, logical nitrogen purge gas is about 20min subsequently; Flask is heated to 130 DEG C and carries out Stille coupling reaction 6h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuo after 50 DEG C of dry 24h, be P3 product, productive rate is 73%.
Test result is: Molecular weight (GPC, THF, R.I): M n=16.1kDa, M w/ M n=2.5
Embodiment 4:
The polymkeric substance containing anthraquinonyl of the present embodiment, i.e. poly-{ 2,6-bis-base-4,8-bis-(5-normal-butyl thiophene) benzene 1,4-Dithiapentalene-co-2,6-bis-base-1,5-bis-(n-decyloxy) anthracene-9,10-diketone } (representing with P4), (wherein, R 1for normal-butyl, R 2for positive decyl, n=97), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen protection, by 2,6-bis-tin trimethyl-4,8-bis-(5-normal butane base thiophene) benzene 1,4-Dithiapentalene (238mg, 0.3mmol), 2,6-bis-bromo-1,5-bis-(n-decyloxy) anthracene-9,10-diketone (259mg, 0.36mmol), three or two argon benzyl acetones two palladium (9mg, 0.009mmol) and 2-dicyclohexyl phosphine-2 ', 6 '-dimethoxy-biphenyl (29mg, 0.072mmol) join in the flask of the DMF filling 12mL, after in flask, logical nitrogen purge gas is about 20min subsequently; Flask is heated to 120 DEG C and carries out Stille coupling reaction 24h.Subsequently, after cooling, stop polyreaction, in flask, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively; Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red powder, after collection under vacuo after 50 DEG C of dry 24h, be P4 product, productive rate is 80%.
Test result is: Molecular weight (GPC, THF, R.I): M n=97.7kDa, M w/ M n=2.0.
Embodiment 5:
The polymkeric substance containing anthraquinonyl of the present embodiment, i.e. poly-{ 2,6-bis-base-4,8-bis-(5-dodecyl thiophene) benzene 1,4-Dithiapentalene-co-2,6-bis-base-1,5-bis-(positive hexyloxy) anthracene-9,10-diketone } (representing with P5), (wherein, R 1for dodecyl, R 2for n-hexyl, n=84), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Under nitrogen and argon gas gas mixture are protected, by 2, 6-bis-tin trimethyl-4, 8-bis-(5-dodecyl thiophene) benzene 1,4-Dithiapentalene (305mg, 0.3mmol), 2, 6-bis-bromo-1, 5-bis-(positive hexyloxy) anthracene-9, 10-diketone (290mg, 0.36mmol) add in the two-mouth bottle of 50mL specification with 15mL toluene, after the gas mixture air-discharging passing into nitrogen and argon gas after abundant dissolving is about 20min, then by tetra-triphenylphosphine palladium (8mg, 0.006mmol) add wherein, after the gas mixture air-discharging of fully logical nitrogen and argon gas is about 10min again, two-mouth bottle is joined 90 DEG C and carry out Stille coupling reaction 48h.Subsequently, after cooling, stop polyreaction, in two-mouth bottle, add 40mL methyl alcohol precipitating, after being filtered by apparatus,Soxhlet's, use methyl alcohol and normal hexane extracting 24h successively.Then be solvent extraction with chloroform to colourless, collect chloroformic solution and be spin-dried for and obtain red solid, after collection, obtain P5 product after 50 DEG C of dry 24h under vacuo.Productive rate is 83%.
Test result is: Molecular weight (GPC, THF, R.I): M n=73.0kDa, M w/ M n=2.1.
Embodiment 6:
Refer to Fig. 2, a kind of organic solar batteries device 60, comprise substrate 61, anode 62, buffer layer 63, active coating 64 and negative electrode 65.Anode 62, buffer layer 63, active coating 64 and negative electrode 65 are formed on substrate 61 successively.
In the present embodiment, substrate 61 is glass.
Anode 62 is formed at a side surface of substrate 61.In the present embodiment, anode 62 is for being ITO(tin indium oxide), preferably, the tin indium oxide of ITO to be square resistance be 10-20 Ω/mouth.
Buffer layer 63 is formed at the side surface of anode 62 away from substrate 61.The material of buffer layer 63 is poly-3,4-Ethylenedioxy Thiophenes (PEDOT) and the mixture of polystyrene-sulfonic acid matrix material (PSS), is expressed as PEDOT:PSS.
Active coating 64 is formed at the side surface of buffer layer 63 away from anode 62.Active coating 64 comprises electron donor material and electron acceptor material, the mol ratio of electron donor material and electron acceptor material is 1:2, wherein electron acceptor material is (6,6) phenyl-C61-methyl-butyrate (PCBM), electron donor material is the polymkeric substance containing anthraquinonyl of the present invention, in the present embodiment, electron donor material is poly-{ 2 of preparation in embodiment 1,6-bis-base-4,8-bis-(5-octane base thiophene) benzene 1,4-Dithiapentalene-co-2,6-bis-base-1,5-bis-(n-octyloxy) anthracene-9,10-diketone } (representing with P1), active coating 64 is expressed as P1:PCBM.
Negative electrode 65 is formed at the side surface of active coating 64 away from buffer layer 63.Negative electrode 65 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 150nm, 130nm or 100nm.In present embodiment, the material of negative electrode 65 is aluminium, and thickness is 170nm.
Be appreciated that buffer layer 63 can omit, now active coating 64 is directly formed at anode 62 surface.
The manufacturing processed of this organic solar batteries 60 is as follows:
Anode 62 is formed at the laggard row ultrasonic cleaning of a side surface of substrate 61, and after processing with oxygen-Plasma, is coated with the PEDOT:PSS formation buffer layer 63 that last layer plays modification on anode 62 surface.
Buffer layer 64 applies one deck active coating 64.This active coating 64 comprises electron donor material and electron acceptor material, and wherein electron acceptor material is PCBM, the P1 of preparation in the embodiment 1 that electron donor material is.
Negative electrode 65 is formed on active coating 64 surface.In present embodiment, negative electrode 65 is the aluminium lamination formed by vacuum evaporation.The thickness of negative electrode 65 is 170nm.
In the present embodiment, this organic solar batteries 60 was through lower 4 hours of 110 degrees Celsius of air tight conditions, drop to room temperature again, the order and regularity that arrange between each group and molecule segment in molecule effectively can be increased after organic solar batteries device is annealed, improve transmission speed and the efficiency of carrier mobility, improve photoelectric transformation efficiency.
At AM1.5G100mW/cm 2under illumination, be the effciency of energy transfer 2.5% of the body heterojunction organic solar batteries 60 of donor material based on the copolymer p 1 in embodiment 1.
When this organic solar batteries device 60 uses, under light illumination, light transmission substrate 61 and anode 62, the conduction hole type solar cell material in active coating 64 absorbs luminous energy, and produces exciton, these excitons move to the interface of electron donor(ED)/acceptor material again, and by transfer transport to electron acceptor material, as PCBM, realize the separation of electric charge, thus form current carrier freely, i.e. electronics and hole freely.These freely electronics to transmit along electron acceptor material to negative electrode 65 and collected by negative electrode, hole to be transmitted and collected by anode 62 along electron donor material anode 62 freely, thus forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load, can power to it.In the process, conduction hole type solar cell material has very wide spectral response range due to it, can utilize luminous energy more fully, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of organic solar batteries.And this organic materials can also alleviate the quality of organic solar batteries, and can be made by technology such as spin coatings, be convenient to large batch of preparation.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Should be understood that, the above-mentioned statement for present pre-ferred embodiments is comparatively detailed, and therefore can not think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.

Claims (9)

1., containing a polymkeric substance for anthraquinonyl, it is characterized in that, its general structure is as follows:
In formula, R 1, R 2be C 1~ C 20alkyl, n is the integer of 13-97.
2. the polymkeric substance containing anthraquinonyl according to claim 1, is characterized in that, R 1for octane base, R 2for octane base, n=35; Or R 1for methyl, R 2for NSC 62789 base, n=62; Or R 1for NSC 62789 base, R 2for methyl, n=13; Or R 1for normal-butyl, R 2for positive decyl, n=97; Or R 1for dodecyl, R 2for n-hexyl, n=84.
3., containing a preparation method for the polymkeric substance of anthraquinonyl, it is characterized in that, comprise the steps:
The compd A providing following structural formula to represent respectively and B,
Under oxygen-free environment, be dissolve mol ratio during the compd A of 1:1 ~ 1.2 and B are added into containing catalyzer organic solvent, Stille coupling reaction is carried out 6 ~ 60 hours at 70 ~ 130 DEG C, polyreaction is stopped after cooling, separating-purifying reaction solution, obtains the described polymkeric substance containing anthraquinonyl of following general structure:
In formula, R 1, R 2be C 1~ C 20alkyl, n is the integer of 13-97.
4. the preparation method of the polymkeric substance containing anthraquinonyl according to claim 3, it is characterized in that, described catalyzer is bis-triphenylphosphipalladium palladium dichloride, tetra-triphenylphosphine palladium; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
5. the preparation method of the polymkeric substance containing anthraquinonyl according to claim 3, it is characterized in that, palladium and the tri-o-tolyl phosphine mixture of described catalyzer to be mol ratio be 1:4 ~ 8, or mol ratio is three or two argon benzyl acetone two palladiums and the 2-dicyclohexyl phosphine-2 of 1:4 ~ 8 ', 6 '-dimethoxy-biphenyl mixture; The mol ratio of described catalyzer and described compd A is 1:20 ~ 1:100.
6. the preparation method of the polymkeric substance containing anthraquinonyl according to claim 3, it is characterized in that, described organic solvent is selected from least one in toluene, DMF, tetrahydrofuran (THF).
7. the preparation method of the polymkeric substance containing anthraquinonyl according to claim 3, is characterized in that, Stille coupling reaction is at 90 ~ 120 DEG C, reacts 12 ~ 48 hours.
8. the preparation method of the polymkeric substance containing anthraquinonyl according to claim 3, it is characterized in that, separating-purifying reaction solution comprises step:
Methyl alcohol precipitating is added in reaction solution, methyl alcohol and normal hexane extracting is used successively after being filtered by apparatus,Soxhlet's, then be that solvent extraction is to colourless with chloroform, collect chloroformic solution and be spin-dried for and obtain powder, powder after collection, more under vacuo after 50 DEG C of dry 24h, obtains the described polymkeric substance containing anthraquinonyl.
9. an organic solar batteries device, is characterized in that, the electron donor material of its active layer adopts the polymkeric substance containing anthraquinonyl of following structural formula:
In formula, R 1, R 2be C 1~ C 20alkyl, n is the integer of 13-97.
CN201310259890.3A 2013-06-26 2013-06-26 Anthraquinonyl group-containing polymer, preparation method thereof, and organic solar cell device Pending CN104250365A (en)

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Publication number Priority date Publication date Assignee Title
CN113861389A (en) * 2021-09-15 2021-12-31 贵州大学 Polymer semiconductors containing quinoid donor-acceptor units, their preparation and use

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CN103159920A (en) * 2011-12-09 2013-06-19 海洋王照明科技股份有限公司 Anthraquinone based co-polymer solar cell material, and preparation method and application thereof

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Publication number Priority date Publication date Assignee Title
CN102060982A (en) * 2010-12-03 2011-05-18 华南理工大学 Organic semiconductor material containing naphthalene [1, 2-c: 5, 6-c] di [1, 2, 5] thiadiazole and application thereof
CN103159920A (en) * 2011-12-09 2013-06-19 海洋王照明科技股份有限公司 Anthraquinone based co-polymer solar cell material, and preparation method and application thereof

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113861389A (en) * 2021-09-15 2021-12-31 贵州大学 Polymer semiconductors containing quinoid donor-acceptor units, their preparation and use
CN113861389B (en) * 2021-09-15 2023-05-02 贵州大学 Polymer semiconductors containing quinone-donor-acceptor units, their preparation and use

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Application publication date: 20141231