CN102372842A - Copolymer containing thiophene pyrroledione units, and preparation method and application thereof - Google Patents
Copolymer containing thiophene pyrroledione units, and preparation method and application thereof Download PDFInfo
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- CN102372842A CN102372842A CN2010102579788A CN201010257978A CN102372842A CN 102372842 A CN102372842 A CN 102372842A CN 2010102579788 A CN2010102579788 A CN 2010102579788A CN 201010257978 A CN201010257978 A CN 201010257978A CN 102372842 A CN102372842 A CN 102372842A
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Abstract
The invention discloses a copolymer containing thiophene pyrroledione units, and a preparation method and application thereof, belonging to the field of photoelectron materials. The copolymer has a general formula (I) as described in the specification, R1, R2 and R3 in the formula are C1-C20 alkyl groups, and n in the formula is an integer in a range of from 1 to 100. Compared to the prior art, the invention has the following advantages: introduction of alkyl groups enables dissolvability and molecular weight of a product to be improved, thereby enabling preparation of polymers or oligomers capable of spin coating to be realized; polymers composed of thiophene pyrroledione monomers and thiophene bithiophene monomers can form a strong donor-acceptor structure, which is favorable for improvement of stability of a material on one hand and reduction of band gaps of the material on the other hand, thereby enlarging an absorption range of sunlight and improving photoelectric conversion efficiency.
Description
Technical field
The present invention relates to a kind of multipolymer, relate to more specifically a kind of be used for organic semiconductor material contain the unitary multipolymer of thiophene pyrrole diketone.
The invention still further relates to a kind of preparation method and application thereof that contains the unitary multipolymer of thiophene pyrrole diketone.
Background technology
Current world economy mainly is to be based upon with fossil energy, like the economy on the bases such as coal, oil and natural gas.Yet these non-renewable fossil energies are all in continuous exhaustion.Got into since 21 century, problems such as global energy problem and consequent environmental pollution and climate warming show especially and aggravation gradually day by day.Because sun power has and distributes general and widely, resource quantity is many, and is pollution-free, cleaning, and safety and obtain outstanding advantages such as convenient is considered to one of renewable energy source the most likely.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, but their price is too expensive, has exceeded the general acceptable degree of present people, this big limitations their use range.In order to reduce the battery cost, expand range of application, for a long time, people are seeking novel solar cell material always.
Organic solar batteries is a kind of novel solar cell, and is limited with respect to the inorganic polymer source, costs an arm and a leg, poisonous; Complicated process of preparation, cost are too high, and it has some incomparable advantages of inorganic solar cell; Extensive like material source, structure diversity and Modulatory character, with low cost; Safety and environmental protection, manufacture craft is simple, and product weight is light; But large area flexible preparation or the like can be widely used in multiple fields such as building, illumination and generating, has important development and application prospect.Therefore, the research institution of lot of domestic and foreign and enterprise etc. have all given suitable concern and input.Yet up to the present, the photoelectric transformation efficiency of organic solar batteries still is much lower than inorganic solar cell.Therefore, the organic polymer of development of new is significant for the efficient that improves organic solar batteries.
Summary of the invention
The object of the present invention is to provide a kind of unitary multipolymer of thiophene pyrrole diketone that contains, in order to address the above problem.
The present invention also aims to provide a kind of preparation method who contains the unitary multipolymer of thiophene pyrrole diketone.
The present invention also aims to provide a kind of unitary multipolymer of thiophene pyrrole diketone that contains at polymer solar battery; Organic field effect tube; Organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser apparatus.
A kind of unitary multipolymer of thiophene pyrrole diketone that contains of the present invention has following general formula (I):
In the formula: R
1, R
2, R
3Be C
1-C
20Alkyl; The span of n is greater than 1 smaller or equal to 100 integer, and the span of preferred n is smaller or equal to 80 integer more than or equal to 20.
The invention still further relates to a kind of above-mentioned preparation scheme that contains the unitary multipolymer of thiophene pyrrole diketone for preparing, it comprises the steps:
Step S1: in the oxygen-free environment, thienothiophene compounds and n-Butyl Lithium (n-BuLi) are added in first solvent with mol ratio 1: 2～4 under-100 ℃～-25 ℃, add trimethyltin chloride (consumption is 2～4 times of thienothiophene compounds molar weight) then; Continue reaction 24～48 hours; Obtain product, promptly 3,6-dialkyl group thieno-[3; 2-b] thiophene-2,5-two bases) two (tin trimethyls); Wherein, first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE, R
1, R
2Be C
1-C
20Alkyl; Its reaction formula is following:
Step S2: with 5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone and 1,3-two bromo-5-alkylthrophenes [3; 4-c]-pyrroles-4,6-diketone (NBS, down together) is added in second solvent with mol ratio 1: 2～4 under 10 ℃～30 ℃; Reacted 12～48 hours, and obtained product, promptly 1; 3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4, the 6-diketone; Wherein, second solvent is the mixed solvent of sulfuric acid and trifluoroacetic acid, R
3Be C
1-C
20Alkyl; Its reaction formula is following:
Step S3: in the oxygen-free environment, with said 3,6-dialkyl group thieno-[3,2-b] thiophene-2; 5-two bases) two (tin trimethyls) and 1,3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4; The 6-diketone is with mol ratio 1: a (wherein, 0.95≤a≤1.05), in the presence of 65 ℃～120 ℃, catalyzer and the 3rd solvent; Carry out Stille reaction 24～72 hours, obtain product, promptly contain thienothiophene and the unitary polymkeric substance of thiophene pyrrole diketone; Wherein, catalyzer is an organic palladium, as, Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2, or organic palladium and organophosphor ligand be 1: 1～10 blended mixtures in molar ratio, as, Pd
2(dba)
3/ P (o-Tol)
3Catalyst consumption is said 3; 6-dialkyl group thieno-[3,2-b] thiophene-2,5-two bases) 0.005-0.20 of two (tin trimethyl) mole dosage doubly; The 3rd solvent is at least a in THF, toluene, trichloromethane or the ETHYLE ACETATE, and the span of n is smaller or equal to 100 integer greater than 1; Its reaction formula is following:
Compared with prior art, major advantage of the present invention is:
1, synthesizing thiofuran thiophthene class monomer, the monomeric route of thiophene pyrrole two ketones are fairly simple and ripe, are prone to help film forming processing through introducing solvability and the molecular weight that alkyl improves product;
2, thienothiophene class monomer is a kind of very excellent donor material; Advantages such as thiophene pyrrole two ketone monomers have simple in structure, symmetrical, and the electron delocalization performance is good, and have two dimensional structure; It is a kind of very excellent acceptor material; The polymkeric substance that is made up of thienothiophene class monomer, thiophene pyrrole two ketones can form a kind of very strong donor-receiver structure, has helped improving the stability of material on the one hand, helps reducing the band gap of material on the other hand; Thereby enlarge the sunshine absorption region, improve electricity conversion;
3, the Suzuki reaction is a kind of very sophisticated polyreaction, and productive rate is high, and mild condition, is easy to control.
Description of drawings
Fig. 1 is to be the structural representation of the organic solar batteries device of active coating with multipolymer of the present invention;
Fig. 2 is to be the structural representation of the organic electroluminescence device of luminescent layer with multipolymer of the present invention;
Fig. 3 is to be the structural representation of the organic field effect tube device of organic semiconductor layer with multipolymer of the present invention.
Embodiment
A kind of unitary multipolymer of thiophene pyrrole diketone that contains provided by the invention has following general formula (I):
In the formula: R
1, R
2, R
3Be C
1-C
20Alkyl; The span of n is greater than 1 smaller or equal to 100 integer, and the span of preferred n be more than or equal to 20 smaller or equal to 80 integer, and preferably the span of n is smaller or equal to 80 integer more than or equal to 20.
The present invention also provides a kind of preparation method who contains the unitary multipolymer of thiophene pyrrole diketone, comprises the steps:
Step S1: in the oxygen-free environment, thienothiophene compounds and n-Butyl Lithium (n-BuLi) are added in first solvent with mol ratio 1: 2～4 under-100 ℃～-25 ℃, add trimethyltin chloride (consumption is 2～4 times of thienothiophene compounds molar weight) then; Continue reaction 24～48 hours; Obtain product, promptly 3,6-dialkyl group thieno-[3; 2-b] thiophene-2,5-two bases) two (tin trimethyls); Wherein, first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE, R
1, R
2Be C
1-C
20Alkyl; Its reaction formula is following:
Step S2: with 5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone and 1,3-two bromo-5-alkylthrophenes [3; 4-c]-pyrroles-4,6-diketone (NBS, down together) is added in second solvent with mol ratio 1: 2～4 under 10 ℃～30 ℃; Reacted 12～48 hours, and obtained product, promptly 1; 3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4, the 6-diketone; Wherein, second solvent is the mixed solvent of sulfuric acid and trifluoroacetic acid, R
3Be C
1-C
20Alkyl; Its reaction formula is following:
Step S3: in the oxygen-free environment, with said 3,6-dialkyl group thieno-[3; 2-b] thiophene-2,5-two bases) two (tin trimethyls) and 1,3-two bromo-5-alkylthrophenes [3; 4-c]-pyrroles-4, the 6-diketone under 65 ℃～120 ℃, carries out Stille reaction 24～72 hours with mol ratio 1: a (0.95＜＜a＜＜1.05) under catalyzer and the 3rd solvent; Obtain product, promptly contain thienothiophene and the unitary semiconductor material of thiophene pyrrole diketone; Wherein, catalyzer is an organic palladium, as, Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2, or organic palladium and organophosphor ligand be 1: 1～10 blended mixtures in molar ratio, as, Pd
2(dba)
3/ P (o-Tol)
3Catalyst consumption is said 3,6-dialkyl group thieno-[3,2-b] thiophene-2; 5-two bases) 0.005-0.20 of two (tin trimethyl) mole dosage doubly; The 3rd solvent is at least a in THF, toluene, trichloromethane or the ETHYLE ACETATE, and the span of n is greater than 1 smaller or equal to 100 integer, and the span of preferred n is smaller or equal to 80 integer more than or equal to 20; Its reaction formula is following:
Oxygen-free environment of the present invention is made up of nitrogen and/or rare gas element.
In order to understand the content of patent of the present invention better, further specify technological case of the present invention through concrete instance and legend below, specifically comprise the preparation of material prepn and device, but these embodiments do not limit the present invention.In the present invention, contain the unitary multipolymer of thiophene pyrrole diketone mainly as organic semiconductor material.
Embodiment 1, present embodiment disclose a kind of structure following contain the unitary multipolymer of thiophene pyrrole diketone:
In the following formula, n=20;
The preparation process of above-mentioned multipolymer is following:
One, the preparation of (3, the 6-thioxene is [3,2-b] thiophene-2 also, 5-two bases) two (tin trimethyls):
Under-100 ℃, condition of nitrogen gas; 40.00mL (1.00M) n-butyllithium solution is added to fills 1.70g 3,6-dimethyl--2,3-dihydro-thiophene also [3; 2-b] in the reaction flask of thiophene and 150mL THF; Stir and slowly drip the 7.96g trimethyltin chloride after 1 hour, return to room temperature, continue to stir 48 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and recrystallization obtains (3, the 6-thioxene is [3,2-b] thiophene-2 also, 5-two bases) two (tin trimethyl) product.
MALDI-TOF-MS(m/z)：493.9(M
+).
Two, 5-thiotolene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.97g thiophene-3, the 4-dicarboxylicacid is added in the 150mL diacetyl oxide under the room temperature, stirs 24 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 150mL toluene, adds the 1.62g methylamine subsequently, is heated to 120 ℃ of reactions 24 hours.Reaction solution is cooled to room temperature, and removal of solvent under reduced pressure adds the 270mL thionyl chloride, is heated to 90 ℃ and refluxes 4 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains 5-thiotolene [3,4-c]-pyrroles-4,6-diketone product.
MALDI-TOF-MS(m/z)：167.2(M
+).
Three, 1,3-two bromo-5-thiotolene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 1.67g 5-thiotolene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 15.3mL sulfuric acid and 50mL trifluoroacetic acid, after stirring 1 hour under 10 ℃, adds 5.34g NBS in batches, continues reaction 24 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains 1,3-two bromo-5-thiotolene [3,4-c]-pyrroles-4,6-diketone solid product.
MALDI-TOF-MS(m/z)：325.0(M
+).
Four, contain the preparation of the unitary multipolymer of thiophene pyrrole diketone:
Under nitrogen protection, toward containing 0.494g (3, the 6-thioxene is [3,2-b] thiophene-2 also, 5-two bases) two (tin trimethyls), 0.325g 1,3-two bromo-5-thiotolene [3,4-c]-pyrroles-4 add 0.018g Pd in 6-diketone, the 25mL reaction of toluene bottle
2(dba)
3With 0.0094g P (o-Tol)
3Behind the nitrogen replacement 1 hour, be heated to 120 ℃, reacted 24 hours.Reaction finishes; Methyl alcohol sedimentation three times; Suction filtration, vacuum-drying obtain structural formula and contain the unitary multipolymer of thiophene pyrrole diketone (n=20) solid product for
.
GPC：Mn＝6669，PDI＝1.7.
Embodiment 2, present embodiment disclose a kind of structure following contain the unitary multipolymer of thiophene pyrrole diketone:
In the following formula, n=55;
The preparation process of above-mentioned multipolymer is following:
One, the preparation of (3,6-dioctyl thieno-[3,2-b] thiophene-2,5-two bases) two (tin trimethyls):
Under-78 ℃, argon gas condition; 10.00mL (2.00M) n-butyllithium solution is added to fills 3.65g 3, in the reaction flask of 4-dioctyl thiophene and 100mL THF, stir and slowly drip the 3.83g trimethyltin chloride after 1 hour; Return to room temperature, continue to stir 36 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and recrystallization obtains (3,6-dioctyl thieno-[3,2-b] thiophene-2,5-two bases) two (tin trimethyl) product.
MALDI-TOF-MS(m/z)：690.3(M
+).
Two, 5-octyl group thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.75g thiophene-3, the 4-dicarboxylicacid is added in the 120mL diacetyl oxide under the room temperature, stirs 22 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 130mL toluene, adds the 6.69g octyl amine subsequently, is heated to 115 ℃ of reactions 26 hours.Reaction solution is cooled to room temperature, and the evaporated under reduced pressure solvent is heated to 90 ℃ and refluxed 6 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains 5-octyl group thiophene [3,4-c]-pyrroles-4,6-diketone product.
MALDI-TOF-MS(m/z)：265.4(M
+).
Three, 1,3-two bromo-5-octyl group thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 2.65g 5-octyl group thiophene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 16.0mL sulfuric acid and 50mL trifluoroacetic acid, after stirring 1 hour under 20 ℃, adds 5.88g NBS in batches, continues reaction 16 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains 1,3-two bromo-5-octyl group thiophene [3,4-c]-pyrroles-4,6-diketone solid product.
MALDI-TOF-MS(m/z)：423.2(M
+).
Four, contain the preparation of the unitary multipolymer of thiophene pyrrole diketone:
Under argon shield, toward containing 0.690g (3,6-dioctyl thieno-[3,2-b] thiophene-2,5-two bases) two (tin trimethyls), 0.420g 1,3-two bromo-5-octyl group thiophene [3,4-c]-pyrroles-4 add 0.0099g Pd in 6-diketone, the 30mL reaction of toluene bottle
2(dba)
3With 0.0079g P (o-Tol)
3Behind the nitrogen replacement 1 hour, be heated to 65 ℃, reacted 72 hours.Reaction finishes; Methyl alcohol sedimentation three times; Suction filtration, vacuum-drying obtain structural formula and contain the unitary multipolymer of thiophene pyrrole diketone (n=55) solid product for
.
GPC：Mn＝34541，PDI＝1.8.
Embodiment 3, present embodiment disclose a kind of structure following contain the unitary multipolymer of thiophene pyrrole diketone:
In the following formula, n=80;
The preparation process of above-mentioned multipolymer is following:
One, the preparation of (3,6-didecyl thieno-[3,2-b] thiophene-2,5-two bases) two (tin trimethyls):
Under-45 ℃, nitrogen and argon gas gas mixture condition; 15.00mL (2.00M) n-butyllithium solution is added to fills 4.21g 3; In the reaction flask of 4-didecyl thiophene and 100mL THF; Stir and slowly drip the 4.97g trimethyltin chloride after 1 hour, return to room temperature, continue to stir 29 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, and recrystallization obtains (3,6-didecyl thieno-[3,2-b] thiophene-2,5-two bases) two (tin trimethyl) product.
MALDI-TOF-MS(m/z)：746.4(M
+).
Two, 5-decylthiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.86g thiophene-3, the 4-dicarboxylicacid is added in the 140mL diacetyl oxide under the room temperature, stirs 28 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 150mL toluene, adds the 6.98g decyl amine subsequently, is heated to 120 ℃ of reactions 24 hours.Reaction solution is cooled to room temperature, and the evaporated under reduced pressure solvent is heated to 90 ℃ and refluxed 10 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains 5-decylthiophene [3,4-c]-pyrroles-4,6-diketone product.
MALDI-TOF-MS(m/z)：293.4(M
+).
Three, 1,3-two bromo-5-decylthiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 2.93g 5-decylthiophene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 18.0mL sulfuric acid and 58mL trifluoroacetic acid, after stirring 1 hour under 25 ℃, adds 5.96g NBS in batches, continues reaction 20 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains 1,3-two bromo-5-decylthiophene [3,4-c]-pyrroles-4,6-diketone solid product.
MALDI-TOF-MS(m/z)：451.2(M
+).
Four, contain the preparation of the unitary multipolymer of thiophene pyrrole diketone:
In the protection of nitrogen and argon gas gas mixture down, past contain 0.746g (3,6-didecyl thieno-[3; 2-b] thiophene-2,5-two bases) two (tin trimethyls), 0.451g 1,3-two bromo-5-decylthiophene [3; 4-c]-pyrroles-4, add 0.0145g Pd in 6-diketone, the 30mL reaction of toluene bottle
2(dba)
3And 0.0124gP (o-Tol)
3Behind the nitrogen replacement 1 hour, be heated to 90 ℃, reacted 48 hours.Reaction finishes; Methyl alcohol sedimentation three times; Suction filtration, vacuum-drying obtain structural formula and contain the unitary multipolymer of thiophene pyrrole diketone (n=80) solid product for
.
GPC：Mn＝56974，PDI＝1.6.
Embodiment 4, present embodiment disclose a kind of structure following contain the unitary multipolymer of thiophene pyrrole diketone:
In the following formula, n=100;
The preparation process of above-mentioned multipolymer is following:
One, the preparation of (3, two icosyl thieno-[3, the 2-b] thiophene-2 of 6-, 5-two bases) two (tin trimethyls):
Under-25 ℃, condition of nitrogen gas; 13.00mL (2.00M) n-butyllithium solution is added to fills 7.01g 3, in the reaction flask of two icosyl thiophene of 4-and 130mL THF, stir and slowly drip the 4.59g trimethyltin chloride after 1 hour; Return to room temperature, continue to stir 38 hours.Reaction finishes, reaction solution poured in the water, and extracted with diethyl ether, anhydrous magnesium sulfate drying revolves steaming, recrystallization obtains 3, two icosyl thieno-[3, the 2-b] thiophene-2 of 6-, 5-two bases) two (tin trimethyl) product.
MALDI-TOF-MS(m/z)：1026.90(M
+).
Two, 5-eicosyl thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 5.23g thiophene-3, the 4-dicarboxylicacid is added in the 100mL diacetyl oxide under the room temperature, stirs 20 hours.Solvent evaporated under reduced pressure with reacting in night is added in the 100mL toluene, adds 14.92g eicosyl amine subsequently, is heated to 115 ℃ of reactions 29 hours.Reaction solution is cooled to room temperature, and the evaporated under reduced pressure solvent is heated to 90 ℃ and refluxed 5 hours.Reaction finishes, and revolves steaming, and column chromatography for separation obtains 5-eicosyl thiophene [3,4-c]-pyrroles-4,6-diketone product.
MALDI-TOF-MS(m/z)：433.7(M
+).
Three, 1,3-two bromo-5-eicosyl thiophene [3,4-c]-pyrroles-4, the preparation of 6-diketone:
With 4.89g 5-eicosyl thiophene [3,4-c]-pyrroles-4, the 6-diketone is added in the mixed solvent of 18.0mL sulfuric acid and 55mL trifluoroacetic acid, after stirring 1 hour under 30 ℃, adds 6.21g NBS in batches, continues reaction 12 hours.Reaction finishes, deionized water wash, and dichloromethane extraction, anhydrous magnesium sulfate drying filters, and revolves steaming, and column chromatography for separation obtains 1,3-two bromo-5-eicosyl thiophene [3,4-c]-pyrroles-4,6-diketone solid product.
MALDI-TOF-MS(m/z)：591.5(M
+)
Four, contain the preparation of the unitary multipolymer of thiophene pyrrole diketone:
Under nitrogen protection, toward contain 1.026g (3, the two icosyl thieno-s [3 of 6-; 2-b] thiophene-2,5-two bases) two (tin trimethyls), 0.596g 1,3-two bromo-5-eicosyl thiophene [3; 4-c]-pyrroles-4, add 0.0125g Pd in 6-diketone, the 25mL reaction of toluene bottle
2(dba)
3With 0.0110g P (o-Tol)
3Behind the nitrogen replacement 1 hour, be heated to 85 ℃, reacted 52 hours.Reaction finishes; Methyl alcohol sedimentation three times; Suction filtration, vacuum-drying obtain structural formula and contain the unitary multipolymer of thiophene pyrrole diketone (n=100) solid product for
.
GPC：Mn＝113296，PDI＝1.5.
The present invention also provides a kind of unitary multipolymer of thiophene pyrrole diketone that contains at polymer solar battery, organic field effect tube, organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser apparatus.
Following examples are to contain the unitary multipolymer of thiophene pyrrole diketone at polymer solar battery, organic field effect tube, organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties and organic laser apparatus.
Embodiment 5
A kind of polymer solar cell device, its structure is as shown in Figure 1.Wherein, the substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this polymer solar cell device is: glass 11/ITO layer 12/PEDOT:PSS layer 13/ active coating 14/Al layer 15; Wherein, the material of active coating 14 is a mixture, comprises electron donor material, and PCBM is an electron acceptor material; Electron donor material is the unitary multipolymer of thiophene pyrrole diketone that contains of the present invention, and electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate (being called for short PCBM); ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is for gathering (3, the 4-Ethylenedioxy Thiophene), and PSS is for gathering (styrene sulfonic acid).
This organic solar batteries preparation of devices process is:
Tin indium oxide (ITO) layer 12 in that surface deposition one deck square resistance of glass substrate 11 is 10-20 Ω/mouth forms as the anodic conductive layer, and thickness is 50-300nm;
Ito glass is through ultrasonic cleaning, and with after oxygen-Plasma processing, plays the PEDOT:PSS layer 13 of modification at ITO surfaces coated last layer, and thickness is 50-300nm;
Adopt spin coating technique to apply layer of active layer 14 at said gathering (3, the 4-Ethylenedioxy Thiophene): PSS on (styrene sulfonic acid) layer for gathering, thickness is 50-300nm; The material of this active coating is for containing the unitary multipolymer of thiophene pyrrole diketone and [6,6] phenyl-C
61The mixture of-methyl-butyrate (being called for short PCBM);
At the surface vacuum evaporation metal aluminium of said active coating, form metal aluminium lamination 15 as negative electrode, obtain said organic solar batteries device;
With the organic solar batteries device with epoxy encapsulation after, place under 120 ℃ of air tight conditions annealing 2 hours, drop to room temperature again.Because after device was annealed, the chemical structure of material was more regular in order, has improved the transmission speed and the efficient of current carrier, thereby has improved the photoelectric transformation efficiency of device.
Wherein, the thickness of ITO, PEDOT:PSS, active coating, Al layer is respectively and is 120nm, 60nm, 100nm, 110nm.
Embodiment 6
A kind of organic electroluminescence device, its structure is as shown in Figure 2; Substrate in the present embodiment adopts ito glass, and glass is as substrate, and ITO is as conductive layer.
The structure of this organic electroluminescence device is: glass 21/ITO layer 22/ luminescent layer 23/LiF impact plies 24/Al layer 25; Wherein: luminescent layer is a material with the unitary multipolymer of thiophene pyrrole diketone that contains of the present invention.
The preparation process of this organic electroluminescence device is:
Tin indium oxide (ITO) layer 22 in that surface deposition one deck square resistance of glass substrate 21 is 10-20 Ω/mouth forms as the anodic conductive layer, and thickness is 50-300nm;
Contain luminescent layer 23 that thiophene pyrrole diketone unitary multipolymer be material at ITO surface preparation one deck with of the present invention through spin coating technique, thickness is 50-300nm;
Vacuum evaporation LiF on luminescent layer, as impact plies 24, thickness is 0.3-2nm;
Vacuum evaporation metallic aluminium on said luminescent layer forms the metal aluminium lamination 25 as negative electrode, obtains said organic electroluminescence device.
Embodiment 7
A kind of organic field effect tube, its structure is as shown in Figure 3; Substrate in the present embodiment adopts doped silicon wafer (Si) as substrate.
The structure of this organic field effect tube is: the SiO that Si 31/450nm is thick
2Insulation layer 32/ is used to modify SiO
2Octadecyl trichlorosilane (OTS) layer 33/ organic semiconductor layer 34/ be source electrode (S) 35 and the drain electrode (D) 36 of material with the gold; Wherein, organic semiconductor layer is a material with the unitary multipolymer of thiophene pyrrole diketone that contains of the present invention; Source electrode (S) and drain electrode (D) also can adopt copper material.
The preparation process of this organic field effect tube is:
At first, on a surface cleaning doped silicon wafer 31, apply one deck SiO later
2 Insulation layer 32; Secondly, at said SiO
2Apply the octadecyl trichlorosilane layer 33 that one deck plays modification on the insulation layer, thickness is 10-200nm; Then, spin coating one deck contains the organic semiconductor layer 34 that the unitary multipolymer of thiophene pyrrole diketone is a material with of the present invention on said octadecyl trichlorosilane layer, and thickness is 50-300nm; At last, on said organic semiconductor layer, being arranged at intervals with the gold is source electrode (S) 35 and the drain electrode (D) 36 of material, obtains said organic field effect tube.
Should be understood that above-mentioned statement to preferred embodiment of the present invention is comparatively detailed, can not therefore 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 accompanying claims.
Claims (10)
- Formula (I) contain the unitary multipolymer of thiophene pyrrole diketone:
In the formula: R 1, R 2, R 3Be C 1-C 20Alkyl; The span of n is smaller or equal to 100 integer greater than 1. - 2. the unitary multipolymer of thiophene pyrrole diketone that contains according to claim 1 is characterized in that, the span of said n is smaller or equal to 80 integer more than or equal to 20.
- 3. a preparation method who contains the unitary multipolymer of thiophene pyrrole diketone is characterized in that, this preparation method comprises the steps:In S1, the oxygen-free environment, do with structural formulaThienothiophene compound and n-Butyl Lithium under-100 ℃～-25 ℃, be added in first solvent with mol ratio 1: 2～4 and react, add trimethyltin chloride then, continue reaction 24～48 hours, obtain structural formula and do
3,6-dialkyl group thieno-[3,2-b] thiophene-2,5-two bases) two (tin trimethyls); Wherein, R 1, R 2Be C 1-C 20Alkyl;
S2, do with structural formula5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone and N-bromo-succinimide are added in second solvent with mol ratio 1: 2～4 under 10 ℃～30 ℃, react 12～48 hours, obtain structural formula and do
1,3-two bromo-5-alkylthrophene [3,4-c]-pyrroles-4,6-diketone; Wherein, R 3Be C 1-C 20Alkyl;
In S3, the oxygen-free environment, catalyzer and the 3rd solvent exist down, with said 3; 6-dialkyl group thieno-[3; 2-b] thiophene-2,5-two bases) two (tin trimethyls) and 1,3-two bromo-5-alkylthrophenes [3; 4-c]-pyrroles-4; The 6-diketone carries out Stille reaction 24～72 hours with mol ratio 1: a under 65 ℃～120 ℃ temperature, obtain said the contain thiophene pyrrole diketone unitary multipolymer of structural formula for; Wherein, the span of a is smaller or equal to 1.05 more than or equal to 0.95; The span of n is smaller or equal to 100 integer greater than 1.
- 4. the preparation method who contains the unitary multipolymer of thiophene pyrrole diketone according to claim 3 is characterized in that, among the step S1, said first solvent is at least a in THF, ether, methylene dichloride, trichloromethane or the ETHYLE ACETATE; The mole dosage of said trimethyltin chloride is 2～4 times of said thienothiophene compound molar weight.
- 5. the preparation method who contains the unitary multipolymer of thiophene pyrrole diketone according to claim 3 is characterized in that, among the said step S2, said second solvent is the mixed solvent of sulfuric acid and trifluoroacetic acid.
- 6. the preparation method who contains the unitary multipolymer of thiophene pyrrole diketone according to claim 3 is characterized in that, among the step S3, said the 3rd solvent is at least a in THF, toluene, trichloromethane or the ETHYLE ACETATE.
- 7. the preparation method who contains the unitary multipolymer of thiophene pyrrole diketone according to claim 3 is characterized in that, among the step S2,Said catalyzer is the mixture of organic palladium or organic palladium and organophosphor ligand; Said catalyst consumption is said 3,6-dialkyl group thieno-[3,2-b] thiophene-2,5-two bases) 0.005～0.2 times of two (tin trimethyl) mole dosage;Said organic palladium is Pd (PPh 3) 4, Pd 2(dba) 3Or Pd (PPh 3) 2Cl 2Said organophosphor ligand is P (o-Tol) 3
- 8. the preparation method who contains the unitary multipolymer of thiophene pyrrole diketone according to claim 8 is characterized in that, in the mixture of said organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1: 1～10.
- 9. the preparation method who contains the unitary multipolymer of thiophene pyrrole diketone according to claim 3 is characterized in that, among the step S3, the span of said n is smaller or equal to 80 integer more than or equal to 20.
- 10. the unitary multipolymer of thiophene pyrrole diketone that contains as claimed in claim 1 is at organic solar batteries, organic field effect tube, organic electroluminescence device, organic optical storage, Application for Field such as organic non-linear optical properties or organic laser apparatus.
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