CN102295748A - Fluorine polymer containing anthracene and pyrrole-pyrrole-dione units and preparation method and use thereof - Google Patents
Fluorine polymer containing anthracene and pyrrole-pyrrole-dione units and preparation method and use thereof Download PDFInfo
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- CN102295748A CN102295748A CN 201010208419 CN201010208419A CN102295748A CN 102295748 A CN102295748 A CN 102295748A CN 201010208419 CN201010208419 CN 201010208419 CN 201010208419 A CN201010208419 A CN 201010208419A CN 102295748 A CN102295748 A CN 102295748A
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- 0 C*(C)c(cc1)cc(C(C)(*)c2c3)c1-c2ccc3-c1c(cccc2)c2c(C(C)(C)C(C)(C)c(cc2C3(C)*)ccc2-c(cc2)c3cc2-c2ccc(C(NC(C3=C(c4ccc(C(C)(C)C(C)(C)C)[s]4)N4)=O)=C3C4=O)[s]2)c(C=C)c1C=C Chemical compound C*(C)c(cc1)cc(C(C)(*)c2c3)c1-c2ccc3-c1c(cccc2)c2c(C(C)(C)C(C)(C)c(cc2C3(C)*)ccc2-c(cc2)c3cc2-c2ccc(C(NC(C3=C(c4ccc(C(C)(C)C(C)(C)C)[s]4)N4)=O)=C3C4=O)[s]2)c(C=C)c1C=C 0.000 description 6
- VAZUEPVAUWTDNL-UHFFFAOYSA-N O=C(C1=C(c([s]2)ccc2Br)N2)NC(c([s]3)ccc3Br)=C1C2=O Chemical compound O=C(C1=C(c([s]2)ccc2Br)N2)NC(c([s]3)ccc3Br)=C1C2=O VAZUEPVAUWTDNL-UHFFFAOYSA-N 0.000 description 2
- RWOOWSACFPOUJD-UHFFFAOYSA-N Fc(ccc1c(c2ccccc22)Br)cc1c2Br Chemical compound Fc(ccc1c(c2ccccc22)Br)cc1c2Br RWOOWSACFPOUJD-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses a fluorine copolymer containing anthracene and pyrrole-pyrrole-dione units and a preparation method and use thereof. The polymer is represented by a formula shown as in the specification. In the formula, R1 and R2 are the same or different and may be H, F, C1 to C20 alkyl or alkoxy; R3 may be H, C1 to C10 alkyl; x+y is equal to 1, x is more than 0, and y more than 0; m is an integer between 1 and 40; and n is an integer between 1 and 200. The fluorine copolymer containing anthracene and pyrrole-pyrrole-dione units is obtained by Suzuki reaction, has a low band gap, a high carrier mobility and a wide light spectrum absorption range, can improve photoelectric conversion efficiency, can be widely used; and in the synthesis method of the fluorine copolymer, the conditions are mild and easy to control.
Description
Technical field
The present invention relates to technical field of polymer materials, relate in particular to a kind of polymkeric substance, its preparation method and application thereof, more particularly, relate to a kind of contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, preparation method and application thereof.
Background technology
Current world economy mainly is that to be based upon fossil energies such as coal, oil and natural gas be economy on the basis, yet the reserves of the fossil energy that these are non-renewable are near exhausted state.Global problem of energy crisis and because of problems such as environmental pollution due to the useization energy and climate warming highlight day by day, and aggravation have gradually been entered since 21 century.Therefore, need seek novel renewable energy source and substitute traditional fossil energy.Outstanding advantages such as that sun power owing to have distributes is wide, resource quantity is many, pollution-free, clean and safe and obtaining makes things convenient for are considered to one of most promising renewable energy source.Solar cell directly changes into electric energy to solar energy, is to utilize the practicable effective ways of sun power.Yet present commercial solar cell also is confined to inorganic solar cell such as silica-based, because their price is too expensive, has exceeded present people's ability to bear, has therefore limited being extensive use of of they greatly.In order to reduce the solar cell cost to expand its range of application, for a long time, people are seeking novel solar cell material always.
Limited with respect to the inorganic semiconductor material of inorganic solar cell source, cost an arm and a leg, poisonous, complicated process of preparation, the too high shortcoming of cost, organic solar batteries is as a kind of novel solar cell, but its have material source extensively, advantage such as simple, the light large area flexible preparation of product weight of structure diversity and Modulatory character, with low cost, safety and environmental protection, manufacture craft, can be widely used in multiple fields such as building, illumination and generating, have important development and application prospect.Yet, up to the present, the photoelectric transformation efficiency of organic solar batteries is well below inorganic solar cell, its main restricting factor for example: spectral response and solar radiation spectrum that organic semiconductor device has lower carrier mobility and organic semiconductor device do not match.Therefore, the semiconductor material of development of new is significant to the photoelectric transformation efficiency that improves organic solar batteries.
Summary of the invention
The technical problem to be solved in the present invention is, at above-mentioned defective of the prior art, a kind of anthracene and unitary fluorene copolymer of pyrrolopyrrole diketone of containing is provided, and it has lower band gap, higher carrier mobility and wide spectral absorption scope, can improve photoelectric transformation efficiency.
The technical problem that the present invention further will solve is, the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone who also provide a kind of mild condition, is easy to control.
The technical problem that the present invention further will solve is, a kind of contain anthracene and the application of the unitary fluorene copolymer of pyrrolopyrrole diketone in preparation organic solar batteries device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties and organic laser apparatus also are provided.
For reaching above-mentioned purpose, according to the present invention, provide a kind of anthracene and unitary fluorene copolymer of pyrrolopyrrole diketone of containing, be the compound of following general formula:
Wherein, R
1And R
2Be expressed as H, F, C identical or differently
1～C
20Alkyl or alkoxyl group, R
3Be expressed as H, C
1～C
10Alkyl, x and y satisfy: x+y=1, x＞0, y＞0, m is 1～40 integer, n is 1～200 integer.
Contain in anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described R
1And R
2Be expressed as H, F, C identical or differently
1～C
10Alkyl or alkoxyl group.
Contain in anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described R
3Be expressed as H, C
1～C
8Alkyl.
Contain in anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described m is 1～10 integer.
Contain in anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described n is 7～50 integer.
For reaching above-mentioned purpose, according to the present invention, also provide a kind of preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone: with 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof, pyrrolopyrrole diketone or derivatives thereof are raw material monomer, join in the organic solvent with catalyzer and alkaline solution, carry out suzuki reaction 12～72h in 60～100 ℃ under oxygen free condition, obtain above-mentioned anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of containing
Described pyrrolopyrrole diketone or derivatives thereof is
The compound of expression.
In the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof, pyrrolopyrrole diketone or derivatives thereof three's mol ratio is 1.0: a: b, a and b satisfy: a＞0, b＞0,0.9≤a+b≤1.1.
In the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described catalyzer is the organic palladium catalyzer, and described catalyst consumption is counted described 2 by molar weight, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.5～10% of 9-dialkyl group fluorenes mole dosage.
In the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, further preferably, described organic palladium catalyzer is three (dibenzalacetones), two palladiums/three (neighbour-tolyl) phosphorus (Pd
2(dba)
3/ P (o-Tol)
3), tetra-triphenylphosphine palladium (Pd (PPh
3)
4) or bi triphenyl phosphorus palladium chloride (Pd (PPh
3)
2Cl
2).
In the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, the described reaction system of keeping is in the pH value and is not more than 10 alkaline environment.
In the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention, preferably, described organic solvent is toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate.
For reaching above-mentioned purpose, according to the present invention, also provide above-mentioned contain anthracene and the application of the unitary fluorene copolymer of pyrrolopyrrole diketone in preparation organic solar batteries device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties and organic laser apparatus.
For reaching above-mentioned purpose, according to the present invention, a kind of organic solar batteries device is provided, comprise substrate layer, first electrode layer, photoactive layer, the second electrode lay, described photoactive layer comprises electron donor material layer and electron acceptor material layer, and described electron donor material layer contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone is made by above-mentioned.
For reaching above-mentioned purpose, according to the present invention, provide a kind of organic electroluminescence device, comprise substrate, anode, luminescent layer, buffer layer, negative electrode, described luminescent layer is to contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone is made by above-mentioned.
For reaching above-mentioned purpose, according to the present invention, a kind of organic field effect tube is provided, comprises silicon substrate, insulation layer, organic semiconductor layer, source electrode and drain electrode, described organic semiconductor layer is to contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone is made by above-mentioned.
Fluorenes class monomer has the chemical structure of easy modification, good thermostability and film-forming properties; Anthracene and derivative thereof have good stability and film-forming properties preferably, the finger peak that its uv-vis spectra presents broad absorbs, help improving the absorption coverage to sunlight, and it has suitable carrier transmission characteristics, hole mobility can reach 3cm under its crystal room temperature
2/ Vs; Pyrrolopyrrole diketone and derivative thereof have high stability to light, heat and different climatopes, but because stronger π-pi-conjugated and molecule hydrogen bond, it is all soluble in most organic solvent, therefore, the present invention introduces the group that increases solubility on 2,5, alkyl for example improves the solubility and the film-forming properties of material, and regulates and control the extinction scope of pyrrolopyrrole diketone by the substituting group that changes 3,6.Therefore, anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of containing of the present invention has lower band gap, higher carrier mobility and wide spectral absorption scope, improved photoelectric transformation efficiency.Of the present inventionly contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone is used for organic solar batteries, behind high temperature annealing, can effectively increase order and the regularity arranged between each group of intramolecularly and molecule segment, improve the transmission speed and the efficient of current carrier, thereby improve photoelectric transformation efficiency.
Of the present inventionly contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone also has satisfactory stability, solvability and workability, can utilize film forming such as whirl coating.
The preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of the present invention has adopted suzuki reaction (Suzuki reaction), and suzuki reaction is a kind of very sophisticated coupling reaction, has productive rate height, reaction conditions gentleness, is easy to advantages such as control.
Anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of containing of the present invention, as a kind of organic semiconductor material, have characteristics such as band gap is low, carrier mobility is high, light abstraction width is wide, workability is good, can be widely used in the photoelectricity technical field, for example the application in preparation organic solar batteries device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties and organic laser apparatus.
Description of drawings
The invention will be further described below in conjunction with drawings and Examples, in the accompanying drawing:
Fig. 1 is for the structural representation that contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone as the organic solar batteries device of photoactive layer of the present invention;
Fig. 2 is for the structural representation that contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone as the organic electroluminescence device of luminescent layer of the present invention;
Fig. 3 is for the structural representation that contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone as the organic field effect tube of organic semiconductor layer of the present invention.
Embodiment
In order to make purpose of the present invention, technical scheme and advantage clearer, the present invention is further described in detail below in conjunction with drawings and Examples.
Of the present inventionly contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone is by 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9, the copolymerization of 10-dibromoanthracene or derivatives thereof and pyrrolopyrrole diketone or derivatives thereof prepares, used three kinds of monomers have had simple, sophisticated preparation technology, can be by preparing voluntarily or obtaining by buying the commercially available prod in the preparation of polymkeric substance.
For example, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes can prepare by the method shown in the following chemical formula:
Under-70 ℃～-85 ℃ anhydrous and oxygen-free reaction conditions, with 2,7-two bromo-9,9-dialkyl group fluorenes and n-Butyl Lithium are added in the solvent with mol ratio 1.0: 2.0～4.0, add 2-isopropoxy-4,4 then, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes or two tetramethyl ethylene ketone close two boron, its consumption counts 2 by mole, 7-two bromo-9,2.0～4.0 times of 9-dialkyl group fluorenes, reacted 12～48 hours, obtain product, promptly 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaborane bases)-9,9-dialkyl group fluorenes.Solvent in this reaction is preferably tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc.
Contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone
Of the present inventionly contain being prepared as follows shown in the formula of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
In the formula, R
1And R
2Be expressed as H, F, C identical or differently
1～C
20Straight chain, band side chain or cyclic alkyl or alkoxyl group, R
3Be expressed as H, C
1～C
10Straight chain, band side chain or cyclic alkyl, x and y satisfy: x+y=1, x＞0, y＞0, m is 1～40 integer, n is 1～200 integer.
Under 60～100 ℃ oxygen free condition, with 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof and pyrrolopyrrole diketone or derivatives thereof join in the mixture of alkaline solution and organic solvent, and carry out Suzuki reaction 12～72 hours in the presence of catalyzer, obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.In this reaction, preferably, described 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof, pyrrolopyrrole diketone or derivatives thereof three's mol ratio is 1.0: a: b, a and b satisfy: a＞0, b＞0,0.9≤a+b≤1.1; Catalyzer is Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2C1
2, alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, organic solvent are toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate etc.Further, catalyst consumption counts 2 by molar weight, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.5%～10% of 9-dialkyl group fluorenes mole dosage.The alkaline solution that adds in this reaction is to be not more than in 10 the alkaline environment in order to make reaction system be in the pH value, and preferably, the consumption of alkaline solution makes reaction system be in the pH value and is not more than 8 weakly alkaline environment.For example, the consumption of alkaline solution can count 2 by molar weight, 7-two (4,4,5,5-tetramethyl--1,3, the assorted oxygen pentaboranes of 2-two) base-9, and 5～10 times of 9-dialkyl group fluorenes mole dosage are in the alkaline environment all the time to guarantee above-mentioned reaction system.
Anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of containing of the present invention, its absorption spectrum is about 310～740nm, and photoabsorption coefficient is 30000M
-1Cm
-1, not only absorption spectrum ranges is wide, and the photoabsorption coefficient height, has improved the utilization ratio of sunlight, thereby has improved photoelectric transformation efficiency.
Embodiment 1 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.1, y=0.9, n=7.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Under the protective condition, in there-necked flask, add 2 of white, 7-two bromo-9; 9-dioctyl fluorene 9.0mmol; then inject 150mL purified tetrahydrofuran solvent, under-78 ℃ of conditions, slowly inject 27.0mmol n-BuLi with syringe more then, stirring reaction 2 hours with syringe.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
Reaction adds the saturated NaCl aqueous solution after finishing, and behind chloroform extraction, anhydrous sodium sulfate drying and suction filtration filtrate collection and rotary evaporation is removed solvent.At last with the crude product sherwood oil: ethyl acetate (v/v=15: 1) separate, obtain pulverulent solids 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene, productive rate 65% for leacheate carries out silica gel column chromatography.GC-MS(EI-m/z)：642(M
+)。
Step 2,3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Under the argon shield condition, in reaction flask, behind the adding 35.7mmol potassium tert.-butoxide, 30mmol 2-cyano thiophene is dissolved in 25mL tertiary amyl alcohol solvent and with syringe it is added to reaction flask, be warming up to 110 ℃.Dropwise join in the reaction system after again the 10mmoL dimethyl succinate being dissolved in 8mL tertiary amyl alcohol solvent, keep dropping and kept thermotonus again 1.5 hours after 1 hour.Continue reaction 2 hours after then by-product carbinol being distilled again.Temperature of reaction system is reduced to 65 ℃ at last, with the dilution of 50mL methyl alcohol, in the acetic acid and after, 10min again refluxes.Obtain black solid behind the suction filtration, the methyl alcohol of reusable heat and deionized water respectively wash 2 times, obtain product 3 after the vacuum-drying, and 6-dithienyl-pyrrolopyrrole diketone can be directly used in next step reaction, productive rate 78% after purifying.Through gas chromatography-mass spectrography (GC-MS) detected result be GC-MS (EI-m/z): 300 (M
+).
Step 3,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
With 3,6-dithienyl-pyrrolopyrrole diketone 8.6mmol and N-bromo-succinimide (NBS) 17.6mmol are dissolved in the 200mL chloroform solvent, are added in two mouthfuls of reaction flasks of argon shield and constantly to stir, and the lucifuge reaction is 50 hours at ambient temperature.Product after the reaction end is joined in the 200mL methanol solvate, have solid to separate out, filter, to leach thing hot washed with methanol 2 times, carry out silica gel column chromatography after the vacuum-drying and purify, obtain solid powdery product 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone, productive rate 75%.GC-MS(EI-m/z)：458(M
+)。
Step 4, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.1mmol, 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.9mmol, tetra-triphenylphosphine palladium (Pd (PPh
3)
4) Na of 0.025mmol, 2mol/L
2CO
3Aqueous solution 5mL and toluene solvant 30mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 90 ℃ of conditions, react 70h.
Behind the reaction 70h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5mL, it is splashed into constantly stirring in the 300mL anhydrous methanol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last with about the extremely surplus 5mL of polymkeric substance/chloroformic solution rotary evaporation, it is splashed in the methanol solvate and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 46300, the polymkeric substance monodispersity is 2.58.
Embodiment 2 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.5, y=0.5, n=46.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees step 2 and the step 3 among the embodiment 1 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.5mmol, 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, other object charging capacity, reaction conditions and post-treating method are seen the step 4 among the embodiment 1, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 57800, the polymkeric substance monodispersity is 2.36.
Embodiment 3 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.8, y=0.2, n=16.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees step 2 and the step 3 among the embodiment 1 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.8mmol, 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.2mmol, Pd (PPh
3)
40.02mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 85 ℃ of conditions, react 48h.Wherein, 9,10-two bromo-2, the synthetic method of 6-two (2-octyl-decyl) anthracene is referring to Macromol.Chem.Phys.2006, and 207,1107-1115.
Behind the reaction 48h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300mL anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the methanol solvate and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.To contain anthracene and the unitary fluorene copolymer extracting of pyrrolopyrrole diketone with Soxhlet extractor, thereby improve the monodispersity of polymericular weight.
With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 78200, the polymkeric substance monodispersity is 2.77.
Embodiment 4 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.2, y=0.8, n=16.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees step 2 and the step 3 among the embodiment 1 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.2mmol, 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.8mmol, other object charging capacity, reaction conditions and post-treating method are seen step 3 among the embodiment 3, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 59600, the polymkeric substance monodispersity is 2.91.
Embodiment 5 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.5, y=0.5, n=18.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Under the protective condition, in there-necked flask, add 2 of white, 7-two bromo-9; 9-didecyl fluorenes 9.0mmol; then inject 200mL purified tetrahydrofuran solvent, under-78 ℃ of conditions, slowly inject 25.0mmol n-BuLi with syringe more then, stirring reaction 2 hours with syringe.React after 2 hours, under-78 ℃ of conditions, inject 28.0mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
Reaction adds the saturated NaCl aqueous solution after finishing, and behind chloroform extraction, anhydrous sodium sulfate drying and suction filtration filtrate collection and rotary evaporation is removed solvent.Be that leacheate carries out silica gel column chromatography and separates with crude product with the mixed solvent of sherwood oil and ethyl acetate at last, obtain pulverulent solids 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes, productive rate 71%.GC-MS(EI-m/z)：699(M
+)。
Step 2,3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation process sees the step 2 among the embodiment 1 for details
Step 3,2,5-dioctyl-3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
With 3; 6-dithienyl-pyrrolopyrrole diketone 43.3mmol and Anhydrous potassium carbonate 24g are dissolved in 250mL N, and the dinethylformamide solvent joins it two mouthfuls of reaction flask post-heating to 140 ℃ under the protection of argon gas; add 1-bromooctane 200mmol, stirring reaction 16 hours with syringe again.Be cooled to room temperature then, there is solid to separate out after pouring reactant into the 500mL frozen water, filter, thing be will leach and deionized water and washed with methanol used for several times, be after washing fluid carries out silica gel column chromatography, to obtain solid powdery product 2,5-dioctyl-3 with methylene dichloride after the vacuum-drying, 6-dithienyl-pyrrolopyrrole diketone, productive rate 71%.GC-MS(EI-m/z)：525(M
+)。
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
With 2; 5-dioctyl-3; 6-dithienyl-pyrrolopyrrole diketone 8.6mmol and N-bromo-succinimide (NBS) 17.6mmol are dissolved in the 200mL chloroform solvent, are added in two mouthfuls of reaction flasks of argon shield and constantly to stir, and the lucifuge reaction is 50 hours at ambient temperature.Product after the reaction end is joined in the 200mL methanol solvate, there is solid to separate out, filter, thing hot washed with methanol 2 times will be leached, carry out silica gel column chromatography after the vacuum-drying and purify, obtain solid powdery product 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone, productive rate 75%.GC-MS(EI-m/z)：682(M
+)。
Step 5, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.5mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, Pd (PPh
3)
40.025mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 88 ℃ of conditions, react 60h.
Behind the reaction 60h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 400mL dehydrated alcohol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the alcohol solvent and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 35900, the polymkeric substance monodispersity is 2.09.
Embodiment 6 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.05, y=0.95, n=38.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details
Step 2,3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation process sees the step 2 among the embodiment 1 for details
Step 3,2,5-dioctyl-3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation process sees the step 3 among the embodiment 5 for details
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees the step 4 among the embodiment 5 for details
Step 5, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.05mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.95mmol, other object charging capacity, reaction conditions and post-treating method are seen the step 5 among the embodiment 5, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 37800, the polymkeric substance monodispersity is 1.84.
Embodiment 7 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.5 in the formula, y=0.5, n=46.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees step 2 and the step 3 among the embodiment 1 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9, (synthetic method of this compound is referring to people's such as Elimelech Rochlin J.Org.Chem., 2003,68 for 10-two bromo-2-fluorine anthracene 0.5mmol, 216-226), 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, Pd (PPh
3)
40.02mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 95 ℃ of conditions, react 58h.
Behind the reaction 58h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300mL anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the methanol solvate and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 58200, the polymkeric substance monodispersity is 2.33.
Embodiment 8 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.6 in the formula, y=0.4, n=17.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees step 2 and the step 3 among the embodiment 1 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2-fluorine anthracene 0.6mmol, 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.4mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone., the polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 51400, the polymkeric substance monodispersity is 2.71.
Embodiment 9 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.5 in the formula, y=0.5, n=50.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees step 2 and the step 3 among the embodiment 1 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-1, (synthetic method of this compound is referring to people's such as Osman Cakmak J.Org.Chem. for 4-dimethoxy anthracene 0.5mmol, 2006,71,1795-1801), 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, Pd (PPh
3)
40.02mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 50mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 95 ℃ of conditions, react 64h.
Behind the reaction 64h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the methanol solvate and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 65600, the polymkeric substance monodispersity is 2.73.
Embodiment 10 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.4 in the formula, y=0.6, n=19.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene:
Its preparation process sees the step 1 among the embodiment 1 for details.
Step 2,3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees step 2 and the step 3 among the embodiment 1 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-1,4-dimethoxy anthracene 0.4mmol, 3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.6mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.Polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 64400, the polymkeric substance monodispersity is 2.21.
Embodiment 11 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.5 in the formula, y=0.5, n=100.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees the step 2, three, four among the embodiment 5 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-2,6-two (eicosyl) anthracene 0.5mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, Pd (PPh
3)
2Cl
20.025mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 60 ℃ of conditions, react 72h.
Behind the reaction 72h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 400ml dehydrated alcohol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the alcohol solvent and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 109000, the polymkeric substance monodispersity is 1.99.
Embodiment 12 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.4 in the formula, y=0.6, n=72.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees the step 2, three, four among the embodiment 5 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (eicosyl) anthracene 0.4mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.6mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.Polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 75800, the polymkeric substance monodispersity is 1.84.
Embodiment 13 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.5 in the formula, y=0.5, n=40.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees the step 2, three, four among the embodiment 5 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-2,6-two (ten alkoxyl groups) anthracene 0.5mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, Pd (PPh
3)
2Cl
20.025mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 100 ℃ of conditions, react 12h.
Behind the reaction 12h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 400ml dehydrated alcohol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the alcohol solvent and stirred for several hour, will contain the unitary fluorene-based polymers of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 37000, the polymkeric substance monodispersity is 1.99.
Embodiment 14 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.1 in the formula, y=0.9, n=62.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees the step 2, three, four among the embodiment 5 for details.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (ten alkoxyl groups) anthracene 0.1mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.9mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain containing anthracene and the unitary fluorene-based polymers of pyrrolopyrrole diketone.Polymkeric substance after purifying is carried out the GPC test, number-average molecular weight Mn ≈ 58900, the polymkeric substance monodispersity is 1.84.
Embodiment 15 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.5 in the formula, y=0.5, n=200.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dimethyl fluorene:
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Under the protective condition, in there-necked flask, add 2 of white, 7-two bromo-9; 9-dimethyl fluorene 9.0mmol; then inject 150mL purified tetrahydrofuran solvent, under-78 ℃ of conditions, slowly inject 27.0mmol n-BuLi with syringe more then, stirring reaction 2 hours with syringe.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
Reaction adds the saturated NaCl aqueous solution after finishing, and behind chloroform extraction, anhydrous sodium sulfate drying and suction filtration filtrate collection and rotary evaporation is removed solvent.At last with the crude product sherwood oil: ethyl acetate (v/v=15: 1) separate, obtain pulverulent solids 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dimethyl fluorene, productive rate 59% for leacheate carries out silica gel column chromatography.GC-MS(EI-m/z)：446(M
+)。
Step 2,3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation process sees the step 2 among the embodiment 1 for details.
Step 3,2,5-dioctyl-3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation process sees the step 3 among the embodiment 5 for details.
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees the step 4 among the embodiment 5 for details.
Step 5, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dimethyl fluorene 1mmol, 9,10-two bromo-2,6-two (2-icosyl) anthracene 0.5mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, Pd (PPh
3)
2Cl
20.045mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 100 ℃ of conditions, react 72h.
Behind the reaction 72h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 400mL dehydrated alcohol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the alcohol solvent and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 335000, the polymkeric substance monodispersity is 2.52.
Embodiment 16 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
X=0.5 in the formula, y=0.5, n=67.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-two tetracontyl fluorenes:
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Under the protective condition, in there-necked flask, add 2 of white, 7-two bromo-9; 9-two tetracontyl fluorenes 9.0mmol; then inject 150mL purified tetrahydrofuran solvent, under-78 ℃ of conditions, slowly inject 27.0mmol n-BuLi with syringe more then, stirring reaction 2 hours with syringe.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
Reaction adds the saturated NaCl aqueous solution after finishing, and behind chloroform extraction, anhydrous sodium sulfate drying and suction filtration filtrate collection and rotary evaporation is removed solvent.At last with the crude product sherwood oil: ethyl acetate (v/v=15: 1) separate, obtain pulverulent solids 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-two tetracontyl fluorenes, productive rate 45% for leacheate carries out silica gel column chromatography.GC-MS(EI-m/z)：1540(M
+)。
Step 2,3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation process sees the step 2 among the embodiment 1 for details.
Step 3,2,5-dioctyl-3, the preparation of 6-dithienyl-pyrrolopyrrole diketone:
Its preparation process sees the step 3 among the embodiment 5 for details.
Step 4,2,5-dioctyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Its preparation process sees the step 4 among the embodiment 5 for details.
Step 5, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-two tetracontyl fluorenes 1mmol, 9,10-two bromo-2,6-two (2-eicosane oxygen base) anthracene 0.5mmol, 2,5-dioctyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, Pd
2(dba)
3/ P (o-Tol)
30.035mmol, the Na of 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 85 ℃ of conditions, react 68h.
Behind the reaction 68h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 400mL dehydrated alcohol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the alcohol solvent and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 261000, the polymkeric substance monodispersity is 2.89.
Embodiment 17 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.5, y=0.5, n=67.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-dimethyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Step 2, three, four in its preparation process reference example 5.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-2,6-two (ten alkoxyl groups) anthracene 0.5mmol, 2,5-dimethyl-3, the Na of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, tetra-triphenylphosphine palladium 0.03mmol, 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 35ml are by leading to N repeatedly
2Make reaction system be in anaerobic state with vacuumizing, under 95 ℃ of conditions, react 48h.
Behind the reaction 48h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 400mL dehydrated alcohol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the alcohol solvent and stirred for several hour, will contain the unitary fluorene-based polymers of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 56000, the polymkeric substance monodispersity is 2.07.
Embodiment 18 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.2, y=0.8, n=50.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-dimethyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Step 2, three, four in its preparation process reference example 5.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (ten alkoxyl groups) anthracene 0.2mmol, 2,5-dimethyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.8mmol, other object charging capacity, reaction conditions and post-treating method are all seen step 3 among the embodiment 17, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 39900, the polymkeric substance monodispersity is 2.36.
Embodiment 19 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.5, y=0.5, n=29.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-didecyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Step 2, three, four in its preparation process reference example 5.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-didecyl fluorenes 1mmol, 9,10-two bromo-2,6-two (ten alkoxyl groups) anthracene 0.5mmol, 2,5-didecyl-3, the Na of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.5mmol, tetra-triphenylphosphine palladium 0.02mmol, 2mol/L
2CO
3Aqueous solution 10mL and toluene solvant 40mL make reaction system be in anaerobic state by leading to N2 repeatedly and vacuumizing, and react 60h under 90 ℃ of conditions.
Behind the reaction 60h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 400mL dehydrated alcohol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove the catalyzer tetra-triphenylphosphine palladium, at last polymkeric substance/chloroformic solution is revolved and steam to remaining about 5mL, it is splashed in the alcohol solvent and stirred for several hour, will contain the unitary fluorene copolymer of anthracene and pyrrolopyrrole diketone at last and collect oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 28000, the polymkeric substance monodispersity is 2.57.
Embodiment 20 contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, and its chemical formula is as follows:
In the formula, x=0.5, y=0.5, n=29.
Step 1,2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-didecyl fluorenes:
Its preparation process sees the step 1 among the embodiment 5 for details.
Step 2,2,5-didecyl-3, the preparation of 6-two (5-bromothiophene) base-pyrrolopyrrole diketone:
Step 2, three, four in its preparation process reference example 5.
Step 3, contain the preparation of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone:
Add 2 in reactor, 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (ten alkoxyl groups) anthracene 0.8mmol, 2,5-didecyl-3,6-two (5-bromothiophene) base-pyrrolopyrrole diketone 0.2mmol, other object charging capacity, reaction conditions and post-treating method are all seen the step 3 among the embodiment 19, then finally obtain containing anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.With after purifying contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone carries out the GPC test, number-average molecular weight Mn ≈ 26900, the polymkeric substance monodispersity is 2.56.
Embodiment 21 organic solar batteries devices
Fig. 1 is for the structural representation that contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone as the organic solar batteries device of photoactive layer of the present invention.
As shown in Figure 1, the structure of this organic solar batteries device is followed successively by from bottom to up: glass/ITO/PEDOT:PSS (poly-(3, the 4-Ethylenedioxy Thiophene): poly-(styrene sulfonic acid))/active coating/PCBM ([6,6] phenyl-C
61-methyl-butyrate)/Al, wherein, the photoactive layer material with the embodiment of the invention 1 contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone is an electron donor material, be electron acceptor material with PCBM, ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth.
This organic solar batteries preparation of devices method is: preparation ITO layer on glass substrate, after ultrasonic cleaning, with oxygen plasma treatment ITO layer, and on the ITO layer, apply PEDOT:PSS, that adopts then that the spin coated technology prepares the embodiment of the invention 1 contains anthracene and unitary fluorene copolymer of pyrrolopyrrole diketone and PCBM layer, respectively as electron donor material and electron acceptor material, on the PCBM layer, prepare metal aluminium electrode by vacuum evaporation technology at last, obtain the organic solar batteries device.
With this organic solar batteries device with epoxy encapsulation after, place 110 ℃ down annealing 24 hours of air tight condition, reduce to room temperature then.After anneal, the chemical structure that contains anthracene and the unitary fluorene copolymer material of pyrrolopyrrole diketone in the organic solar batteries device is more regular in order, has improved the transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Embodiment 22 organic electroluminescence devices
Fig. 2 is for the structural representation that contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone as the organic electroluminescence device of luminescent layer of the present invention.
As shown in Figure 2, this organic electroluminescence device comprises glass substrate, ITO layer, luminescent layer, LiF buffer layer and aluminium electrode layer, wherein, luminescent layer be the embodiment of the invention 1 contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.
The preparation method of this organic electroluminescence device is: deposition one deck square resistance is that the ITO of 10-20 Ω/mouth is as transparent anode on glass substrate, contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone as luminescent layer by what the spin coated technology prepared one deck embodiment of the invention 1 on ITO then, again on this luminescent layer vacuum evaporation LiF as buffer layer, last evaporation metal Al obtains organic electroluminescence device as negative electrode.
Embodiment 23 organic field effect tubes
Fig. 3 is for the structural representation that contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone as the organic field effect tube of organic semiconductor layer of the present invention.
As shown in Figure 3, this organic field effect tube comprises silicon substrate, insulation layer, organic semiconductor layer, source electrode and drain electrode, wherein, organic semiconductor layer be the embodiment of the invention 1 contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone.
The preparation method of this organic field effect tube is: adopt highly doped silicon chip Si as substrate, with the thick SiO of 500nm
2As insulation layer, and it is modified, utilize contain the SiO that anthracene and pyrrolopyrrole diketone unitary fluorene copolymer preparation at OTS modify of spin coated technology then the embodiment of the invention 1 with octadecyl trichlorosilane (OTS)
2Above the layer, form two gold electrodes at last, obtain organic field effect tube respectively as source electrode S and drain electrode D.
The above only is representative embodiment of the present invention, does not limit the present invention in any way, and all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces or improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, it is characterized in that, is the compound of following general formula:
Wherein, R
1And R
2Be selected from H, F, C
1～C
20Alkyl or alkoxyl group, R
3Be selected from H, C
1～C
10Alkyl, x and y satisfy: x+y=1, x＞0, y＞0, m is 1～40 integer, n is 1～200 integer.
2. anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of containing according to claim 1 is characterized in that described R
1And R
2Be selected from H, F, C
1～C
10Alkyl or alkoxyl group, described R
3Be expressed as H, C
1～C
8Alkyl.
3. anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone of containing according to claim 1 is characterized in that described m is 1～10 integer, and described n is 7～50 integer.
4. a preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone is characterized in that, with 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof, pyrrolopyrrole diketone or derivatives thereof are raw material monomer, join in the organic solvent with catalyzer and alkaline solution, under oxygen free condition, carry out suzuki reaction 12～72h in 60～100 ℃, obtain structural formula and be expressed as
Contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone,
Described pyrrolopyrrole diketone or derivatives thereof is
The compound of expression, wherein, R
1And R
2Be selected from H, F, C
1～C
20Alkyl or alkoxyl group, R
3Be selected from H, C
1～C
10Alkyl, x and y satisfy: x+y=1, x＞0, y＞0, m is 1～40 integer, n is 1～200 integer.
5. the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone according to claim 4 is characterized in that described 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dialkyl group fluorenes, 9,10-dibromoanthracene or derivatives thereof, pyrrolopyrrole diketone or derivatives thereof three's mol ratio is 1.0: a: b, a and b satisfy: a＞0, b＞0,0.9≤a+b≤1.1.
6. according to claim 4 or the 5 described preparation methods that contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, it is characterized in that, described catalyzer is the organic palladium catalyzer, and described catalyst consumption is counted described 2 by molar weight, and 7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,0.5～10% of 9-dialkyl group fluorenes mole dosage.
7. the preparation method who contains anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone according to claim 6 is characterized in that described organic palladium catalyzer is Pd
2(dba)
3/ P (o-Tol)
3, Pd (PPh
3)
4Or Pd (PPh
3)
2Cl
2
8. according to claim 4 or the 5 described preparation methods that contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, it is characterized in that described alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution, described alkaline solution are kept reaction system and are in the pH value and are not more than 10 alkaline environment.
9. according to claim 4 or the 5 described preparation methods that contain anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone, it is characterized in that described organic solvent is toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane or ethyl acetate.
10. each describedly contains the application in preparation organic solar batteries device, organic field effect tube, organic electroluminescence device, organic light storage device, organic non-linear optical properties and organic laser apparatus of anthracene and the unitary fluorene copolymer of pyrrolopyrrole diketone according to claim 1～3.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103360397A (en) * | 2013-07-11 | 2013-10-23 | 华南理工大学 | Bithienyl pyrrolopyrroledione-naphthyl conjugated derivative as well as preparation method and application thereof |
| CN104017178A (en) * | 2013-02-28 | 2014-09-03 | 海洋王照明科技股份有限公司 | Polymer containing diketopyrrolopyrrole group as well as preparation method and application thereof |
| CN106057863A (en) * | 2016-08-15 | 2016-10-26 | 深圳市华星光电技术有限公司 | Multi-primary-color OLED display device |
| CN115873250A (en) * | 2023-01-01 | 2023-03-31 | 湖南工业大学 | Black polyimide containing pyrrolopyrroledione structure and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101407574A (en) * | 2008-12-01 | 2009-04-15 | 中国科学院长春应用化学研究所 | Donor-receptor type conjugated polymer containing dithiophen b pyrrole, preparation method and application thereof |
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2010
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101407574A (en) * | 2008-12-01 | 2009-04-15 | 中国科学院长春应用化学研究所 | Donor-receptor type conjugated polymer containing dithiophen b pyrrole, preparation method and application thereof |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104017178A (en) * | 2013-02-28 | 2014-09-03 | 海洋王照明科技股份有限公司 | Polymer containing diketopyrrolopyrrole group as well as preparation method and application thereof |
| CN103360397A (en) * | 2013-07-11 | 2013-10-23 | 华南理工大学 | Bithienyl pyrrolopyrroledione-naphthyl conjugated derivative as well as preparation method and application thereof |
| CN103360397B (en) * | 2013-07-11 | 2016-03-02 | 华南理工大学 | Dithienyl pyrrolo-pyrrole-dione-naphthyl conjugate derivative and its preparation method and application |
| CN106057863A (en) * | 2016-08-15 | 2016-10-26 | 深圳市华星光电技术有限公司 | Multi-primary-color OLED display device |
| CN106057863B (en) * | 2016-08-15 | 2019-05-31 | 深圳市华星光电技术有限公司 | More primary colors OLED displays |
| CN115873250A (en) * | 2023-01-01 | 2023-03-31 | 湖南工业大学 | Black polyimide containing pyrrolopyrroledione structure and preparation method and application thereof |
| CN115873250B (en) * | 2023-01-01 | 2024-04-05 | 湖南工业大学 | Black polyimide containing pyrrolopyrrole diketone structure and preparation method and application thereof |
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