CN102295752A - Dithiophene silole-thiophene-quinoxaline conjugate polymer and preparation method as well as application thereof - Google Patents
Dithiophene silole-thiophene-quinoxaline conjugate polymer and preparation method as well as application thereof Download PDFInfo
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- CN102295752A CN102295752A CN2010102103127A CN201010210312A CN102295752A CN 102295752 A CN102295752 A CN 102295752A CN 2010102103127 A CN2010102103127 A CN 2010102103127A CN 201010210312 A CN201010210312 A CN 201010210312A CN 102295752 A CN102295752 A CN 102295752A
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- 0 CC(C(C)(C)C)c1cc([n](C)c2c3[n]c(C(C)(C)*(C)(*)C4=CC(C)C(C(C)(C)C(C)(C)c5c(*)c(*)c(C(C)(C)C(C)(C)C)[n]5)C5=C4*C(*)=C(*)*5)c2)c3[n]1 Chemical compound CC(C(C)(C)C)c1cc([n](C)c2c3[n]c(C(C)(C)*(C)(*)C4=CC(C)C(C(C)(C)C(C)(C)c5c(*)c(*)c(C(C)(C)C(C)(C)C)[n]5)C5=C4*C(*)=C(*)*5)c2)c3[n]1 0.000 description 6
- NTLWHMCRFSCKHS-DXNYSGJVSA-N C/C=N\c1cc([n](c2c3[nH]c(C)c2)I)c3[nH]1 Chemical compound C/C=N\c1cc([n](c2c3[nH]c(C)c2)I)c3[nH]1 NTLWHMCRFSCKHS-DXNYSGJVSA-N 0.000 description 1
- XHNQOLJUJHSXST-UHFFFAOYSA-N CCC(C)(C)CNc1cc(CCN)c(-c([nH]c([N](C)(C)C)c2)c2NI)[nH]1 Chemical compound CCC(C)(C)CNc1cc(CCN)c(-c([nH]c([N](C)(C)C)c2)c2NI)[nH]1 XHNQOLJUJHSXST-UHFFFAOYSA-N 0.000 description 1
- YPWQGWIWKBGKEQ-UHFFFAOYSA-N CCCCCCCC[S+](c1c-2[s]c([Sn](C)(C)C)c1)c1c-2[s]c([Sn](C)(C)C)c1 Chemical compound CCCCCCCC[S+](c1c-2[s]c([Sn](C)(C)C)c1)c1c-2[s]c([Sn](C)(C)C)c1 YPWQGWIWKBGKEQ-UHFFFAOYSA-N 0.000 description 1
- GGWKNPNIYLAWHT-UHFFFAOYSA-N CCCCCCCC[Si](C)(c1c-2[s]c([Sn](C)(C)C)c1)c1c-2[s]c([Sn](C)(C)C)c1 Chemical compound CCCCCCCC[Si](C)(c1c-2[s]c([Sn](C)(C)C)c1)c1c-2[s]c([Sn](C)(C)C)c1 GGWKNPNIYLAWHT-UHFFFAOYSA-N 0.000 description 1
- OGWOWIOVYDZNRB-UHFFFAOYSA-N CCCCCC[n]1c(cc(cc2)C(C(c3ccccc3)=O)=O)c2c2ccccc12 Chemical compound CCCCCC[n]1c(cc(cc2)C(C(c3ccccc3)=O)=O)c2c2ccccc12 OGWOWIOVYDZNRB-UHFFFAOYSA-N 0.000 description 1
- FEVAOCRCMDXWDO-UHFFFAOYSA-N CCCCCC[n]1c2cc(-c(c(-c3ccccc3)nc3c(cc4)Br)nc3c4[Br]=C)ccc2c2ccccc12 Chemical compound CCCCCC[n]1c2cc(-c(c(-c3ccccc3)nc3c(cc4)Br)nc3c4[Br]=C)ccc2c2ccccc12 FEVAOCRCMDXWDO-UHFFFAOYSA-N 0.000 description 1
- VPMJBJSLTPBZLR-UHFFFAOYSA-N Nc(c(Br)ccc1Br)c1N Chemical compound Nc(c(Br)ccc1Br)c1N VPMJBJSLTPBZLR-UHFFFAOYSA-N 0.000 description 1
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
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- Y02E10/549—Organic PV cells
Abstract
The invention discloses dithiophene silole-thiophene-quinoxaline conjugate polymer and a preparation method as well as application thereof. The polymer has a molecular structural general formula (I), wherein x+y+z is equal 2; x is more than or equal to 1; z is more than 0 and is less than 1; y is more than 0 and is less than 1; n is an integer and is more than 1 and is less than or equal to 150; R1 is selected from C1-C20 alkyl groups; R2 and R3 are selected from -H, C1-C20 alkyl groups, C1-C20 alkoxyl groups, alkyl group or alkoxyl group-containing benzene ring groups, alkyl group-containing fluorene groups or alkyl group-containing carbazole groups; and R4 and R5 are selected from -H, C1-C20 alkyl groups or C1-C20 alkoxyl groups. The copolymer has high crystallinity, good charge transfer characteristic, thermal stability, environmental stability, superior electrochemical reducing property, capabilities of weakening double-molecule compounding, increasing carrier mobility and widening spectral response, simple preparation process, high yield and easiness in operation and control.
Description
Technical field
The invention belongs to the organic compound synthesis technical field, relate to specifically a kind ofly contain two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers and its production and application.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is the research focus and the difficult point in photovoltaic field always.The silicon solar cell that is used for ground at present is restricted its application owing to complex manufacturing, cost height.In order to reduce cost, expand range of application, people are seeking novel solar cell material always for a long time.Polymer solar battery receives much concern because of advantage such as mode large-area preparation such as cheap, the light weight of cost of material, flexibility, simple, the available coating of production technique, printing, if its energy conversion efficiency can be brought up to the level near the commodity silicon solar cell, its market outlook will be very huge.From report conjugated polymers and C on SCIENCE such as N.S.Sariciftci in 1992
60Between photoinduction transfer transport phenomenon after, people have dropped into big quantity research aspect polymer solar battery, and have obtained development at full speed.At present, the research of polymer solar battery mainly concentrates on to body, acceptor co-mixing system, adopts PTB7 and PC
71The energy conversion efficiency of BM co-mixing system has reached 7.4%, but it is still much lower than the efficiency of conversion of inorganic solar cell, the main restricting factor that limiting performance improves has: the carrier mobility that organic semiconductor device is relatively low, the spectral response of device and solar radiation spectrum do not match, the red light district of high photon flux be not used effectively and the electrode collection effciency of current carrier low etc.In order to make polymer solar battery obtain actual application, the material of development of new increases substantially the top priority that its effciency of energy transfer is still this research field.
Summary of the invention
The objective of the invention is to overcome the above-mentioned deficiency of prior art, providing a kind of contains two thiophene thiophenes and coughs up-thiophene-quinoxaline conjugated polymers, this conjugation is poly-by cyclopentadienedithiderivatives structural unit, quinoxaline structural unit, the copolymerization of thiophene structural unit are formed conjugated polymers, thereby improved the crystal property of this polymkeric substance, improved the transport property of electric charge, it is compound to have weakened bimolecular, increased carrier mobility, widen spectral response, had good thermostability and environmental stability and excellent electrochemical reduction character.
Another object of the present invention is to provide that a kind of technology is simple, productive rate is high, be easy to operate and control contain two thiophene thiophenes and cough up-preparation method of thiophene-quinoxaline conjugated polymers.
Further aim of the present invention is to provide above-mentioned and contains two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device or/and the application in the organic laser apparatus.
In order to realize the foregoing invention purpose, technical scheme of the present invention is as follows:
A kind ofly contain two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers, its general formula of molecular structure is following (I):
In the formula, x+y+z=2, and x 〉=1,0＜z＜1,0＜y＜1; N is an integer, and 1＜n≤150; R
1Be selected from C
1～C
20Alkyl; R
2, R
3Be selected from-H, C
1～C
20Alkyl, C
1～C
20Alkoxyl group, contain alkyl or alkoxy benzene cyclic group, contain the alkyl fluorene group or contain the alkyl carbazole group; R
4, R
5Be selected from-H, C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
And, a kind ofly contain two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, comprise the steps:
The compd A, B, C, the D that provide following structural formula to represent respectively,
Wherein, R
1Be selected from C
1～C
20Alkyl; R
2, R
3Be selected from-H, C
1～C
20Alkyl, C
1～C
20Alkoxyl group, contain alkyl or alkoxy benzene cyclic group, contain the alkyl fluorene group or contain the alkyl carbazole group; R
4, R
5Be selected from-H, C
1～C
20Alkyl or C
1～C
20Alkoxyl group;
Under the condition that oxygen-free environment catalyst neutralisation, organic solvent exist, choose compd A, B, C, D and carry out the Stille coupling reaction, obtain following general structure and be the containing two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers of (I) expression,
In the general structure (I), x+y+z=2, and x 〉=1,0＜z＜1,0＜y＜1; N is integer and 1＜n≤150.
Further, the present invention contain two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device or/and the application in the organic laser apparatus.
The present invention compared with prior art possesses following advantage at least:
This contain two thiophene thiophenes and cough up-two thiophene that contain in the quinoxaline conjugated polymers molecule have particular structure, two thiphene ring in its structural unit are on same plane, thereby effectively prolonged the conjugation performance of polymkeric substance, reduce the energy gap of polymkeric substance, make current carrier between two main chains, shift to become and be more prone to, increased carrier mobility; It is with cyclopentadiene (2 that the two thiophene thiophenes that contain are coughed up the unit, 1-b:3,4-b ') the C atom in the structure of two thiophene converts the Si atom to, thereby effectively improved the crystal property of this polymkeric substance, improved the transport property of electric charge, it is compound to have weakened bimolecular, mixes the back charge transfer complex with soccerballene and reduces, and makes the carrier mobility that the carrier mobility of this polymkeric substance relatively only contains two thiophen polymers exceed an order of magnitude;
2. the thiophene structural unit that also contains simultaneously has five-membered ring structure, meets shock youngster rule, and therefore, the existence of this thiophene structural unit makes this polymkeric substance also have moderate band gap, the spectral response of broad, thermostability and environmental stability preferably;
3. described polymkeric substance also contains the quinoxaline structural unit, is the good body unit that is subjected to strong electron-withdrawing power, thereby makes polymkeric substance have high electric transmission character, high second-order transition temperature, excellent electrochemical reduction character; And quinoxaline unit can utilize easy method to introduce electron-donating group and electron-accepting group, regulates its electrophilic performance, thereby makes polymkeric substance of the present invention also have the stronger chemistry and the modifiability of structure;
4. contain two thiophene thiophenes to cough up-thiophene-quinoxaline conjugated polymers is owing to comprise two thiophene thiophenes simultaneously and cough up structural unit, quinoxaline structural unit and thiophene structural unit, taken into account three's performance advantage, thus effectively expanded this polymkeric substance at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device or/and the application in the organic laser apparatus;
The preparation of described polymkeric substance by with the measured response thing in suitable reaction environment, make target product thereby just can react by controlled temperature, therefore, preparation technology is simple, is easy to operate and control, and is suitable for suitability for industrialized production.
Description of drawings
Fig. 1 is the synoptic diagram of the containing two thiophene thiophenes and cough up of the embodiment of the invention-thiophene-quinoxaline conjugated polymers general formula of molecular structure;
Fig. 2 is so that the containing two thiophene thiophenes and cough up of embodiment 1 preparation-thiophene-quinoxaline conjugated polymers is the structural representation of the polymer solar cell device of active coating;
Fig. 3 is so that the containing two thiophene thiophenes and cough up of embodiment 1 preparation-thiophene-quinoxaline conjugated polymers is the structural representation of the organic electroluminescence device of active coating;
Fig. 4 is so that the containing two thiophene thiophenes and cough up of embodiment 1 preparation-thiophene-quinoxaline conjugated polymers is the structural representation of the organic field effect tube device of organic semiconductor layer.
Embodiment
In order to make the technical problem to be solved in the present invention, technical scheme and beneficial effect clearer,, the present invention is further elaborated below in conjunction with embodiment.Should be appreciated that specific embodiment described herein only in order to explanation the present invention, and be not used in qualification the present invention.
See also Fig. 1, what show the embodiment of the invention a kind ofly contains two thiophene thiophenes and coughs up-thiophene-quinoxaline conjugated polymers general formula of molecular structure, and it is following (I):
In the formula, x+y+z=2, and x 〉=1,0＜z＜1,0＜y＜1; N is an integer, and 1＜n≤150; R
1Be selected from C
1～C
20Alkyl; R
2, R
3Be selected from-H, C
1～C
20Alkyl, C
1～C
20Alkoxyl group, contain alkyl or alkoxy benzene cyclic group, contain the alkyl fluorene group or contain the alkyl carbazole group; R
4, R
5Be selected from-H, C
1～C
20Alkyl or C
1～C
20Alkoxyl group.R
1Be preferably C
4～C
20Alkyl, R
2, R
3Be preferably C
4～C
20Alkyl, C
4～C
20Alkoxyl group, contain alkyl or alkoxy benzene cyclic group, R
4, R
5Be preferably C
4～C
20Alkyl, C
4～C
20Alkoxyl group, this R
1, R
2, R
3, R
4, R
5The preferred group of institute can effectively improve present embodiment and contains two thiophene thiophenes and cough up-solvability of thiophene-quinoxaline conjugated polymers, and n is preferably 10～100.
The above-mentioned preferred structure general formula that contains the alkyl fluorene group is as follows, in the formula, and R
6, R
7Group for identical or inequality is preferably C
1～C
15Alkyl,
The described preferred structure general formula that contains the alkyl carbazole group is as follows, in the formula, and R
8Be preferably C
1～C
15Alkyl,
The described preferred structure general formula that contains alkyl or alkoxy benzene cyclic group is as follows, in the formula, and R
9Preferred C
1～C
15Alkyl or C
1～C
15Alkoxyl group,
Containing alkyl or alkoxy benzene cyclic group, contain the alkyl fluorene group or containing the existence of alkyl carbazole group of above-mentioned preferred structure general formula can increase the cloud density of present embodiment polymkeric substance on the one hand, helps its absorbing wavelength red shift, in addition, and R
6, R
7, R
8Or R
9The introducing of group helps improving its solvability.
Above-mentionedly contain two thiophene thiophenes and cough up-two thiophene that contain in the quinoxaline conjugated polymers molecule have particular structure, two thiphene ring in its structural unit are on same plane, thereby effectively prolonged the conjugation performance of polymkeric substance, reduce the energy gap of polymkeric substance, make current carrier between two main chains, shift to become and be more prone to, increased carrier mobility; It is with cyclopentadiene (2 that the two thiophene thiophenes that contain are coughed up the unit, 1-b:3,4-b ') the C atom in the structure of two thiophene converts the Si atom to, thereby effectively improved the crystal property of this polymkeric substance, improved the transport property of electric charge, it is compound to have weakened bimolecular, mixes the back charge transfer complex with soccerballene and reduces, and makes the carrier mobility that the carrier mobility of this polymkeric substance relatively only contains two thiophen polymers exceed an order of magnitude; Enlarged its range of application in fields such as organic solar batteries.
The foregoing description is described to be contained two thiophene thiophenes and coughs up-and the thiophene structural unit that also contains simultaneously in thiophene-quinoxaline conjugated polymers molecule has five-membered ring structure, meet shock youngster rule, therefore, the existence of this thiophene structural unit, make this polymkeric substance also have moderate band gap, the spectral response of broad, thermostability and environmental stability have effectively been expanded the application of this polymkeric substance in the photovoltaic field preferably;
Above-mentioned polymkeric substance also contains the quinoxaline structural unit, is the good body unit that is subjected to strong electron-withdrawing power, thereby makes polymkeric substance have high electric transmission character, high second-order transition temperature, excellent electrochemical reduction character; And quinoxaline unit can utilize easy method to introduce electron-donating group and electron-accepting group, regulates its electrophilic performance, thereby makes polymkeric substance of the present invention also have the stronger chemistry and the modifiability of structure.
Present embodiment also provides above-mentioned and contains two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, comprises the steps:
1) compd A, B, C, the D that provides following structural formula to represent respectively,
Wherein, R
1Be selected from C
1～C
20Alkyl; R
2, R
3Be selected from-H, C
1～C
20Alkyl, C
1～C
20Alkoxyl group, contain alkyl or alkoxy benzene cyclic group, contain the alkyl fluorene group or contain the alkyl carbazole group; R
4, R
5Be selected from-H, C
1～C
20Alkyl or C
1～C
20Alkoxyl group;
2) under the condition that oxygen-free environment catalyst neutralisation, organic solvent exist, choose compd A, B, C, D and carry out the Stille coupling reaction, obtain following general structure containing two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers for (I) expression.Step 2) Stille Coupled with Chemical Reaction formula can be expressed as follows:
In the general structure (I), x+y+z=2, and x 〉=1,0＜z＜1,0＜y＜1; N is an integer, and 1＜n≤150.
In the above-mentioned steps (1), compd A can but be not limited to obtain as the method for step 3) among the embodiment 1; Compound D can but be not limited to obtain as the method for step 3) among the embodiment 1; Compd B can make according to the following steps: under the condition that lucifuge condition and 0～50 ℃ and organic solvent exist, with mol ratio 2～3: 1 NBS and 4,4-dialkyl group two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up and carries out bromination reaction, obtains described compd B, and wherein organic solvent is tetrahydrofuran (THF), chloroform, methylene dichloride or N, at least a in the dinethylformamide, the bromination reaction time is preferably 0.5～48 hour; Preparation method's preferred version of Compound C is: under the condition that 20～120 ℃ and organic solvent exist, with cyclohexadione compounds and 3,6-dibromo O-Phenylene Diamine compound is 1: 0.1～10 to carry out condensation reaction 1～24h in molar ratio, make described Compound C, the organic solvent of condensation reaction described in the preparation method of Compound C is at least a in acetate, m-cresol, tosic acid, chloroform, methyl alcohol, ethanol, the butanols, and its consumption should guarantee carrying out smoothly of this dehydration reaction at least.
In the above-mentioned steps (2), the Stille coupling reaction needs catalyzer, because this Stille coupling reaction needs participating in of catalyzer, in described Stille coupling reactions, produce intermediate product with a reactant wherein, make this Stille coupling reaction finally can realize.The catalyzer addition is preferably 0.05%～50% of compd A molar percentage, and this catalyzer is the mixture of organic palladium catalyzer or organic palladium catalyzer and organophosphorus ligand, and wherein, the organic palladium catalyzer is preferably Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2In at least a, organophosphorus ligand is preferred but be not limited only to P (o-Tol)
3When catalyzer was the mixture of organic palladium catalyzer and organophosphorus ligand, the mol ratio of organic palladium catalyzer and organophosphorus ligand was preferably 1: 2-20.Organic solvent in this Stille coupling reaction is preferably one or more in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene, the toluene, and the temperature of reaction is preferably 50～150 ℃, and the time is preferably 24～72 hours.
In the above-mentioned steps (2), the Stille coupling reaction also need carry out in oxygen-free environment, this is because reactant and oxygen chemical property in the Stille coupling reaction are all very active, after participating in oxygen in the reaction environment, oxygen preferably with reactant reaction, oxygen has destroyed the formation of intermediate product simultaneously, thereby causes the failure of this Stille coupling reaction.This oxygen-free environment can adopt vacuum or be full of rare gas element and realize, preferably is full of rare gas element and realizes oxygen-free environment, and this rare gas element is a present technique field rare gas element commonly used, for example nitrogen, argon gas etc., preferred nitrogen.
In the above-mentioned steps (2), compd A, B, C, D four reactant consumption mol ratios are preferred k: i: m: p, and k=i+m+p, wherein, and k 〉=m+p＞0, m＞0, p＞0, i 〉=0.In general structure (I), x+y+z=2, and x 〉=1,0＜z＜1,0＜y＜1; N is an integer, and 1＜n≤150, can release thus: p＞0, m＞0, k=i+m+p＞0, i 〉=0.When i=0, k=m+p＞0 that is to say that reactant is that A, C, D three reactants participate in the Stille coupling reaction, as step 4) among the embodiment 1; When i＞0, k=i+m+p＞0 that is to say that reactant is that A, B, C, D four reactants participate in the Stille coupling reaction, as step 4) among the embodiment 4.
Contain two thiophene thiophenes at this to cough up-thiophene-quinoxaline method for preparing conjugated polymer in, only need reactant press the ratio interpolation, need not special equipment and environmental requirement, its preparation method technology is simple, productive rate height, and mild condition, be easy to operate and control, be suitable for suitability for industrialized production.
Above-mentioned provide contain two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers coughs up structural unit, quinoxaline structural unit and thiophene structural unit owing to comprise two thiophene thiophenes simultaneously, taken into account three's performance advantage, for example good solubility, carrier mobility, thermostability, environmental stability and stronger chemistry is arranged and the structure modifiability, thus effectively expanded this polymkeric substance at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device or/and the application in the organic laser apparatus.
Now in conjunction with the embodiments, the present invention is further elaborated.
Embodiment 1
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2,3 pair (phenyl replacement) quinoxaline conjugated polymers, and the following I of its structural formula
1Shown in,
Its preparation process is as follows:
1) compound 2, the preparation of 5-two bromo-4,5 dioctyl thiophene, and its chemical equation is as follows:
The preparation detailed process is: with NBS (2.9g, 16.3mmol) join and contain 3, (2.1g is in DMF 6.8mmol) (50mL) solution for 4-dioctyl thiophene, stirring at room 12 hours, reaction solution is poured in the saturated aqueous common salt, carries out chloroform extraction, saturated common salt water washing successively, rotary evaporation removes to desolvate and obtains thick product, thick product is obtained the oily product by column chromatography (sherwood oil is as eluent), and productive rate 76% records MS (EI) m/z:466 (M of this product
+).
2) compound 5,8-two bromo-2, and the preparation of two (phenyl) quinoxalines of 3-, its chemical equation is as follows:
The preparation detailed process is: under 120 ℃, with 3,6-two bromo-O-Phenylene Diamine (1.0g, 3.7mmol) join compound diphenylthanedione (0.39g, 1.84mmol) acetate (20mL) solution in, refluxed 15 hours, reaction solution is poured in the water, be neutralized to neutrality with sodium bicarbonate, adopt chloroform extraction, saturated common salt water washing, anhydrous sodium sulfate drying, rotary evaporation remove the thick product that arrives that desolvates, thick product column chromatography is got white solid, chloroform/normal hexane recrystallization obtains the white solid powdered product then, and its productive rate 86% records MS (EI) m/z:440 (M of this product
+);
3) 4,4 '-two (eicosyl)-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] preparations that thiophene is coughed up of 6-, its chemical equation is as follows:
The preparation detailed process is: will be under-78 ℃, with t-BuLi (5.3mL, 1.4mol/L, 7.5mmol) be added drop-wise to 4,4 '-eicosyl-two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up that (2.6mmol in tetrahydrofuran solution 1.1g) (100mL), is slowly returning to room temperature with the mixed solution of gained, stir 0.5h, be cooled to-78 ℃ again, with trimethyltin chloride (7.5mmol, 7.5mL) be added drop-wise in the above-mentioned solution after, slowly recover room temperature, stirred 13 hours, with the cancellation of above-mentioned reaction solution water, rotary evaporation is removed tetrahydrofuran (THF), the chloroform/water extraction, water washing, anhydrous sodium sulfate drying is removed organic phase and is obtained solid product, its productive rate 49% records MS (MALDI) m/z:744 (M of this product
+);
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2,3 couple (phenyl replacement) quinoxaline conjugated polymers I
1Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection, toward containing compound 5,8-two bromo-2; two (phenyl) quinoxalines of 3-(0.11g, 0.25mmol), 2,5-two bromo-3; 4-dioctyl thiophene (0.12g; 0.25mmol), 4,4 '-two (eicosyl)-2, two tin trimethyl-two thiophene [3 of 6-; 2-b:2 '; 3 '-d] thiophene coughs up that (0.52g, bubbling inflated with nitrogen 0.5h removes the oxygen in the environment in chlorobenzene 0.5mmol) (25mL) solution, adds Pd again
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, be heated to 60 ℃ then and refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, again with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 64%, record this product molecular weight Molecular weight (GPC, THF, R.I): M
n=63,700, M
w/ M
n=2.3).
Embodiment 2
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2,3 pair (phenyl replacement) quinoxaline conjugated polymers, and the following I of its structural formula
2Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to step 1) is identical among the embodiment 1 preparation method and similar reaction conditions, 5-two bromo-3,4-two hot alkoxy thiophenes,
2) according to step 2 among the embodiment 1) identical preparation method and similarly reaction conditions prepare structural formula following 5,8-two bromo-2-(4-n-butylphenyl) 3-(4-eicosane oxygen base phenyl) quinoxaline,
3) according to step 3) is identical among the embodiment 1 preparation method and similarly reaction conditions prepare structural formula following 4,4 '-di-n-butyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) cyclopentadiene (2,1-b:3,4-b ') two thiophene-thiophene-2,3 couple (phenyl replacement) quinoxaline conjugated polymers I
2Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection; toward containing compound 5; 8-two bromo-2-(4-n-butylphenyl) 3-(4-eicosane oxygen base phenyl) quinoxaline (0.40g; 0.25mmol), 2; 5-two bromo-3; 4-two hot alkoxy thiophene (0.124g; 0.25mmol), 4; 4 '-di-n-butyl-2; two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up (0.32g; 0.5mmol) glycol dimethyl ether (25mL) solution in bubbling inflated with nitrogen 0.5h remove oxygen in the environment, add Pd again
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, be heated to 60 ℃ then and refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, again with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 69%, record this product Molecular weight (GPC, THF, R.I): M
n=37,500, M
w/ M
n=2.1).
Embodiment 3
The preparation of cyclopentadiene (2,1-b:3,4-b ') two thiophene-thiophene-2,3 pair (phenyl replacement) quinoxaline conjugated polymers, the following I of its structural formula
3Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to step 1) is identical among the embodiment 1 preparation method and similar reaction conditions, 5-two bromo-3,4-two fourth alkoxy thiophenes,
2) according to step 2 among the embodiment 1) identical preparation method and similarly reaction conditions prepare structural formula following 5,8-two bromo-2-(4-NSC 62789 base phenyl)-3-(4-normal butane oxygen base phenyl) quinoxaline,
3) according to step 3) is identical among the embodiment 1 preparation method and similarly reaction conditions prepare structural formula following 4,4 '-di-n-butyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2,3 couple (phenyl replacement) quinoxaline conjugated polymers I
3Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection, toward containing compound 5,8-two bromo-2-(4-NSC 62789 base phenyl)-3-(4-normal butane oxygen base phenyl) quinoxaline (0.40g; 0.25mmol), 2; 5-two bromo-3, and 4-two fourth alkoxy thiophenes (0.1g, 0.25mmol), 4; 4 '-di-n-butyl-2; two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up (0.37g; 0.5mmol) chlorobenzene (25mL) solution in bubbling inflated with nitrogen 0.5h remove oxygen in the environment, add Pd again
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, be heated to 50 ℃ then and refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, again with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 56%, record this product Molecular weight (GPC, THF, R.I): M
n=43,500, M
w/ M
n=1.9).
Embodiment 4
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2,3 pair (phenyl replacement) quinoxaline conjugated polymers, and the following I of its structural formula
4Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to step 1) is identical among the embodiment 1 preparation method and similar reaction conditions, 5-two bromo-3,4-two (NSC 62789 base) thiophene,
2) according to step 2 among the embodiment 1) identical preparation method and similarly reaction conditions prepare structural formula following 5,8-two bromo-2-3-phenylbenzene quinoxalines,
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2,3 couple (phenyl replacement) quinoxaline conjugated polymers I
4Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection; toward containing compound 5; 8-two bromo-2-3-phenylbenzene quinoxaline (0.011g; 0.025mmol), 2,5-two bromo-3,4-two (NSC 62789 base) thiophene (0.02g; 0.025mmol), 4; 4 '-dioctyl-2, and 6-two bromo-two thiophene [3,2-b:2 '; 3 '-d] thiophene coughs up (0.25g; 0.45mmol), 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3 of 6-; 2-b:2 '; 3 '-d] thiophene coughs up that (0.37g, bubbling inflated with nitrogen 0.5h removes the oxygen in the environment in chlorobenzene 0.5mmol) (25mL) solution, adds Pd again
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, be heated to 60 ℃ then and refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, again with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 73%, record this product Molecular weight (GPC, THF, R.I): M
n=53,000, M
w/ M
n=1.7).
Embodiment 5
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2-phenyl-3-carbazyl quinoxaline conjugated polymers, and the following I of its structural formula
5Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to step 1) is identical among the embodiment 1 preparation method and similar reaction conditions, 5-two bromo-3, two (the NSC 62789 oxygen base) thiophene of 4-,
2) 5, the preparation of 8-two bromo-2-phenyl-3-(nitrogen-hexyl carbazole) base-quinoxaline, its chemical equation is as follows:
The preparation detailed process is: under 120 ℃, with 3,6-two bromo-O-Phenylene Diamine (1.0g, 3.7mmol) join compound 2-(3-(nitrogen hexyl carbazole) base) benzene second diketone (0.68g, 1.78mmol) acetate (20mL) solution in, reflux and after 15 hours reaction solution is poured in the water, be neutralized to neutrality with sodium bicarbonate, carry out chloroform extraction, saturated common salt water washing more successively, anhydrous sodium sulfate drying, rotary evaporation removes to desolvate and obtains thick product, and thick product column chromatography is got white solid, and chloroform/normal hexane recrystallization obtains the pressed powder product then, its productive rate 67% records MS (MALDI) m/z:614 (M of this product
+);
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2-phenyl-3-carbazyl quinoxaline conjugated polymers I
5Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection; toward containing compound 5; 8-two bromo-2-phenyl-3-(nitrogen-hexyl carbazole) base-quinoxaline (0.15g; 0.25mmol); 2; 5-two bromo-3; two (the NSC 62789 oxygen base) thiophene of 4-(0.21g, 0.25mmol), 4; 4 '-dioctyl-2; two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up (0.37g; 0.5mmol) 1: 1 by volume tetrahydrofuran (THF) and the mixed solvent (25mL) of benzene in bubbling inflated with nitrogen 0.5h remove oxygen in the environment, add Pd (PPh again
3)
2Cl
2(0.035mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, being heated to 50 ℃ then refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours again, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 63%, record this product Molecular weight (GPC, THF, R.I): M
n=42,500, M
w/ M
n=1.9).
Embodiment 6
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2-phenyl-3-carbazyl quinoxaline conjugated polymers, and the following I of its structural formula
6Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to step 1) is identical among the embodiment 1 preparation method and similar reaction conditions, 5-two bromo-3, two (normal-butyl) thiophene of 4-,
2) according to step 2 among the embodiment 2) identical preparation method and similarly reaction conditions prepare structural formula following 5,8-two bromo-2-phenyl-3-(nitrogen NSC 62789 base carbazole) base-quinoxaline,
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2-phenyl-3-carbazyl quinoxaline conjugated polymers I
6Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection; under nitrogen protection; toward containing compound 5; 8-two bromo-2-phenyl-3-(nitrogen NSC 62789 base carbazole) base-quinoxaline (0.21g; 0.25mmol), 2; 5-two bromo-3; two (normal-butyl) thiophene (0.088g of 4-; 0.25mmol), 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3 of 6-; 2-b:2 '; 3 '-d] thiophene coughs up that (0.37g, bubbling inflated with nitrogen 0.5h removes the oxygen in the environment in tetrahydrofuran (THF) 0.5mmol) (25mL) solution, adds Pd (PPh again
3)
2Cl
2(0.035mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, being heated to 130 ℃ then refluxed 24 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours again, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 67%, record this product Molecular weight (GPC, THF, R.I): M
n=27,000, M
w/ M
n=1.7).
Embodiment 7
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2-phenyl-3-carbazyl quinoxaline conjugated polymers, and the following I of its structural formula
7Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to the preparation method that step 1) is identical among the embodiment 1,5-two bromo-3,4-dioctyl thiophene,
2) according to step 2 among the embodiment 2) identical preparation method and similarly reaction conditions prepare structural formula following 5,8-two bromo-2-phenyl-3-(nitrogen normal-butyl carbazole) base-quinoxaline,
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2-phenyl-3-carbazyl quinoxaline conjugated polymers I
7Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection; toward containing compound 5; 8-two bromo-2-phenyl-3-(nitrogen normal-butyl carbazole) base-quinoxaline (0.15g; 0.25mmol), 2; 5-two bromo-3; 4-dioctyl thiophene (0.12g; 0.25mmol), 4; 4 '-dioctyl-2; two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up (0.37g; 0.5mmol) volume ratio be that bubbling inflated with nitrogen 0.5h removes oxygen in the environment in 1: 1 benzene and the mixed solvent of toluene (25mL) solution, add Pd (PPh again
3)
2Cl
2(0.035mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, being heated to 60 ℃ then refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours again, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 56%, record this product Molecular weight (GPC, THF, R.I): M
n=48,500, M
w/ M
n=2.1).
Embodiment 8
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-thiophene-and, 3 couples of (preparation of (2-(9,9-two substituted fluorenes) base) quinoxaline conjugated polymers, the following I of its structural formula
8Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to step 1) is identical among the embodiment 1 preparation method and similar reaction conditions, 5-two bromo-3-octyl group thiophene,
2) 5,8-dibromo 2,3-pair (preparation of (2-(9, the 9-dioctyl fluorene) base)-quinoxaline, its chemical equation is as follows:
The preparation detailed process is: under 120 ℃, with 3,6-two bromo-O-Phenylene Diamine (0.5g, 1.85mmol) join compound two (9, the 9-dioctyl fluorene) (0.42g in acetate 5.0mmol) (20mL) solution, refluxes after 15 hours for basic second diketone, reaction solution is poured in the water, be neutralized to neutrality with sodium bicarbonate, carry out chloroform extraction, saturated common salt water washing more successively, anhydrous sodium sulfate drying, rotary evaporation removes to desolvate and obtains thick product, and thick product column chromatography gets white solid, and chloroform/normal hexane recrystallization obtains the pressed powder product then, its productive rate 81% records MS (MALDI) m/z:1065.2 (M+) of this product;
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) cyclopentadiene (2,1-b:3,4-b ') two thiophene-thiophene-3 couple ((2-(9,9-two substituted fluorenes) base) quinoxaline conjugated polymers I
8Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection, toward containing compound 5,8-dibromo 2; 3-two ((2-(9, the 9-dioctyl fluorene) base)-quinoxaline (and 0.27g, 0.25mmol), 2; 5-two bromo-3-octyl group thiophene (0.088g; 0.25mmol), 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3 of 6-; 2-b:2 '; 3 '-d] thiophene coughs up that (0.37g, bubbling inflated with nitrogen 0.5h removes the oxygen in the environment in toluene 0.5mmol) (30mL) solution, adds Pd (PPh again
3)
4(0.025mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, being heated to 150 ℃ then refluxed 24 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours again, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.After the gained solid extracted 72 hours with the acetone Soxhlet, carry out methyl alcohol sedimentation, suction filtration successively, obtain product, its productive rate 62%, record this product Molecular weight (GPC, THF, R.I): M
n=93,500, M
w/ M
n=2.1).
Embodiment 9
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-thiophene-and, 3 couples of (preparation of (2-(9,9-two substituted fluorenes) base) quinoxaline conjugated polymers, the following I of its structural formula
9Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to the preparation method that step 1) is identical among the embodiment 1,5-two bromo-3,4-dioctyl thiophene,
2) according to step 2 among the embodiment 8) identical preparation method and similarly reaction conditions prepare structural formula following 5,8-two bromo-2-(9, the 9-dioctyl fluorene) base)-3-((2-(9,9-two NSC 62789 base fluorenes) base)-quinoxaline, its chemical equation is as follows:
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene cough up-thiophene-, 3 couples of ((2-(9,9-two substituted fluorenes) base) quinoxaline conjugated polymers I
9Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection; toward containing compound 5; 8-two bromo-2-(9; the 9-dioctyl fluorene) base)-((2-(9 for 3-; 9-two NSC 62789 base fluorenes) base)-quinoxaline (0.32g; 0.25mmol), 2; 5-two bromo-3, and 4-dioctyl thiophene (0.12g, 0.25mmol), 4; 4 '-dioctyl-2; two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up (0.37g; 0.5mmol) toluene (30mL) solution in bubbling inflated with nitrogen 0.5h remove oxygen in the environment, add Pd (PPh again
3)
4(0.025mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, being heated to 85 ℃ then refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours again, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.The gained solid, is carried out methyl alcohol sedimentation, suction filtration successively, obtains product, its productive rate 69% after 72 hours with the extraction of acetone Soxhlet.Record this product Molecular weight (GPC, THF, R.I): M
n=94,500, M
w/ M
n=2.3).
Embodiment 10
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2,3 dialkyl group quinoxaline conjugated polymers, and the following I of its structural formula
10Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to the preparation method that step 1) is identical among the embodiment 1,5-two bromo-3,4-dioctyl thiophene,
2) 5,8-two bromo-2, the preparation of 3-dioctyl quinoxaline, its chemical equation is as follows:
The preparation detailed process is: under 120 ℃, with 3,6-two bromo-O-Phenylene Diamine (0.5g, 1.85mmol) join compound dioctyl second diketone (0.28g, in acetate 1mmol) (30mL) solution,, after 12 hours reaction solution is poured in the water through back flow reaction, be neutralized to neutrality with sodium bicarbonate, carry out chloroform extraction more successively, saturated common salt water washing, anhydrous sodium sulfate drying, rotary evaporation remove desolvate thick product, thick product column chromatography gets white solid, chloroform/normal hexane recrystallization obtains the product of wanting then, and its productive rate 80% records MS (EI) m/z:512 (M of this product
+);
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2,3 dialkyl group quinoxaline conjugated polymers I
10Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection, toward containing compound 5,8-two bromo-2; 3-dioctyl-quinoxaline (0.13g, 0.25mmol), 2,5-two bromo-3; 4-dioctyl thiophene (0.12g; 0.25mmol), 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3 of 6-; 2-b:2 '; 3 '-d] thiophene coughs up that (0.37g, bubbling inflated with nitrogen 0.5h removes the oxygen in the environment in toluene 0.5mmol) (30mL) solution, adds Pd again
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, be heated to 70 ℃ then and refluxed 72 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, again with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.The gained solid, is carried out methyl alcohol sedimentation, suction filtration successively, obtains product, its productive rate 53% after 72 hours with the extraction of acetone Soxhlet.Record this product Molecular weight (GPC, THF, R.I): M
n=52,000, M
w/ M
n=2.1).
Two thiophene [3,2-b:2 ', 3 '-d] thiophene coughs up-preparation of thiophene-2,3 dialkyl group quinoxaline conjugated polymers, and the following I of its structural formula
11Shown in,
Its preparation process is as follows:
1) prepare the following compound of structural formula 2 according to the preparation method that step 1) is identical among the embodiment 1,5-two bromo-3,4-dioctyl thiophene,
2) according to step 2 among the embodiment 10) identical preparation method and similarly reaction conditions prepare structural formula following 5,8-two bromo-2-NSC 62789 base-3-methyl-quinoxalines,
3) according to the preparation method of step 3) among the embodiment 3 prepare structural formula following 4,4 '-dioctyl-2, two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up,
4) two thiophene [3,2-b:2 ', 3 '-d] thiophene is coughed up-thiophene-2,3 dialkyl group quinoxaline conjugated polymers I
11Synthetic, its chemical equation is as follows:
The preparation detailed process is: under nitrogen protection, toward containing compound 5,8-two bromo-2-NSC 62789 base-3-methyl-quinoxaline (0.15g; 0.25mmol), 2; 5-two bromo-3, and 4-dioctyl thiophene (0.12g, 0.25mmol), 4; 4 '-dioctyl-2; two tin trimethyl-two thiophene [3,2-b:2 ', the 3 '-d] thiophenes of 6-are coughed up (0.37g; 0.5mmol) toluene (30mL) solution in bubbling inflated with nitrogen 0.5h remove oxygen in the environment, add Pd again
2(dba)
3(0.014g, 0.015mmol) and P (o-Tol)
3(0.0083g, 0.027mmol), continue bubbling inflated with nitrogen 1h and remove residual oxygen, be heated to 125 ℃ then and refluxed 36 hours, with the mixed solution that obtains be added drop-wise to carry out sedimentation in the methyl alcohol after, carry out suction filtration, methanol wash, drying successively, again with joining in the aqueous solution of Thiocarb after the chlorobenzene dissolving, then mixed solution is heated to 80 ℃ and stirs standing demix after 12 hours, with the column chromatography of organic phase by aluminum oxide, chloroform drip washing.Reduce pressure successively then and remove organic solvent, methyl alcohol sedimentation, suction filtration and get solid.The gained solid, is carried out methyl alcohol sedimentation, suction filtration successively, obtains product, its productive rate 59% after 72 hours with the extraction of acetone Soxhlet.Record this product Molecular weight (GPC, THF, R.I): M
n=47,500, M
w/ M
n=1.9).
Application Example 12
With the preparation of the polymkeric substance of embodiment 1 preparation as the solar cell device of active coating:
See also Fig. 2, this solar cell device comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14, the negative electrode 15 that stacks gradually, middle supplementary layer 13 adopts polyethylene dioxy base thiophene: polystyrene-sulfonic acid matrix material (abbreviating PEDOT:PSS as), active coating 14 comprises electron donor material and electron acceptor material, electron donor material adopts the polymkeric substance of embodiment 1 preparation, electron acceptor material can be [6,6] phenyl-C
61-methyl-butyrate (abbreviating PCBM as).Transparent anode 12 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, for example Ca/Al or Ba/Al etc.Wherein, glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, handle with oxygen-Plasma, supplementary layer 13 in the middle of applying on ito glass on the supplementary layer 13, forms active coating 14 in the middle of the polymkeric substance of embodiment 1 preparation and electron acceptor material being coated on after by blend again, and then, obtain above-mentioned solar cell device by vacuum evaporation technology deposition cathode 15 on active coating 14.In a preferred embodiment, the thickness of transparent anode 12, middle supplementary layer 13, active coating 14, double-metal layer Ca and Al layer be respectively 170,40,150,70nm.
As shown in Figure 2, under illumination, light transmission glass-base 11 and ITO electrode 12, the polymkeric substance of embodiment 1 preparation in the active coating 14 absorbs luminous energy, and produces exciton, these excitons are moved to electron donor(ED)/acceptor material at the interface again, and give electron acceptor material with transfer transport, as PCBM, realize the separation of electric charge, thereby form current carrier freely, i.e. electronics and hole freely.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, freely the hole along electron donor material to ito anode transmission and collected by anode, thereby form photoelectric current and photovoltage, realize opto-electronic conversion, during external load 16, can power to it.In this process, the polymkeric substance of embodiment 1 preparation can utilize luminous energy more fully because it has very wide spectral response range, to obtain higher photoelectric transformation efficiency, increases the electricity generation ability of solar cell device.And this organic materials can also alleviate the quality of solar cell device, and can make by technology such as spin coatings, is convenient to large batch of preparation.
Application Example 13
The polymer organic electroluminescence preparation of devices that contains embodiment 1 preparation:
See also Fig. 3, show the polymer organic electroluminescence device that adopts embodiment 1 preparation, it comprises glass-base 21, transparent anode 22, luminescent layer 23, buffer layer 24, the negative electrode 25 that is cascading.Transparent anode 22 can adopt tin indium oxide (abbreviating ITO as), is preferably the tin indium oxide that square resistance is 10-20 Ω/.Luminescent layer 23 comprises the polymkeric substance of embodiment 1 preparation.Buffer layer 24 can adopt LiF etc., but is not limited thereto.Negative electrode 25 can be but be not limited to metal A l etc.Thereby in a specific embodiment, the organic electroluminescence device structural table is shown: the polymkeric substance/LiF/Al of ITO/ embodiment 1 preparation.Each layer can adopt existing method to form, and the polymkeric substance of embodiment 1 preparation can be formed on the ITO by spin coating technique.On this luminescent layer, can adopt vacuum evaporation LiF buffer layer, on buffer layer, can adopt evaporation metal Al, as the negative electrode of device.
Application Example 14
Contain the preparation of the polymer organic field-effect transistor of poly-embodiment 1 preparation:
See also Fig. 4, this organic field effect tube comprises substrate 31, insulation layer 32, decorative layer 33, the organic semiconductor layer 34 that is cascading and is located at source electrode 35 and drain electrode 36 on the organic semiconductor layer 34.Wherein, substrate 31 can be but be not limited to highly doped silicon chip (Si) that insulation layer 32 can be but be not limited to micro-nano (as 450nm) thick SiO
2 Organic semiconductor layer 34 adopts the polymerised moiety of embodiment 1 preparation.Source electrode 35 and drain electrode 36 all can adopt but be not limited to gold.Decorative layer 33 can be but be not limited to octadecyl trichlorosilane (OTS).Substrate 31, insulation layer 32, decorative layer 33 and source electrode 35 and drain electrode 36 all can adopt existing method to form.Organic semiconductor layer 34 can be that the polymkeric substance that embodiment 1 prepares is spun on the insulation layer of being modified by decorative layer 33 32.
The above only is preferred embodiment of the present invention, not in order to restriction the present invention, all any modifications of being done within the spirit and principles in the present invention, is equal to and replaces and improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. one kind contains two thiophene thiophenes and coughs up-thiophene-quinoxaline conjugated polymers, and its general formula of molecular structure is following (I):
In the formula, x+y+z=2, and x 〉=1,0＜z＜1,0＜y＜1; N is an integer, and 1＜n≤150; R
1Be selected from C
1～C
20Alkyl; R
2, R
3Be selected from-H, C
1～C
20Alkyl, C
1～C
20Alkoxyl group, contain alkyl or alkoxy benzene cyclic group, contain the alkyl fluorene group or contain the alkyl carbazole group; R
4, R
5Be selected from-H, C
1～C
20Alkyl or C
1～C
20Alkoxyl group.
2. according to claim 1ly contain two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers, it is characterized in that:
It is described that to contain alkyl fluorene group general structure as follows, in the formula, and R
6, R
7Be C identical or inequality
1～C
15Alkyl,
It is described that to contain alkyl carbazole unit structure general formula as follows, in the formula, and R
8Be selected from C
1～C
15Alkyl,
Describedly contain alkyl or alkoxy benzene cyclic group general structure is as follows, in the formula, R
9Be selected from C
1～C
15Alkyl or C
1～C
15Alkoxyl group,
3. one kind contains two thiophene thiophenes and coughs up-thiophene-quinoxaline method for preparing conjugated polymer, comprises the steps:
The compd A, B, C, the D that provide following structural formula to represent respectively,
Wherein, R
1Be selected from C
1～C
20Alkyl; R
2, R
3Be selected from-H, C
1～C
20Alkyl, C
1～C
20Alkoxyl group, contain alkyl or alkoxy benzene cyclic group, contain the alkyl fluorene group or contain the alkyl carbazole group; R
4, R
5Be selected from-H, C
1～C
20Alkyl or C
1～C
20Alkoxyl group;
Under the condition that oxygen-free environment catalyst neutralisation, organic solvent exist, choose compd A, B, C, D and carry out the Stille coupling reaction, obtain following general structure and be the containing two thiophene thiophenes and cough up-thiophene-quinoxaline conjugated polymers of (I) expression,
In the general structure (I), x+y+z=2, and x 〉=1,0＜z＜1,0＜y＜1; N is an integer, and 1＜n≤150.
4. according to claim 3ly contain two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, it is characterized in that: the preparation method of described Compound C comprises following steps:
Under the condition that 20～120 ℃ and organic solvent exist, with cyclohexadione compounds and 3,6-dibromo O-Phenylene Diamine compound is 1: 0.1～10 to carry out condensation reaction 1～24h in molar ratio, makes described Compound C.
5. according to claim 4ly contain two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, it is characterized in that: the organic solvent of described condensation reaction is at least a in acetate, m-cresol, tosic acid, chloroform, methyl alcohol, ethanol, the butanols.
6. according to claim 3ly contain two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, it is characterized in that: the mol ratio of compd A, B, C, D four reactant consumptions is k: i: m: p in the described Stille coupling reaction, wherein, k 〉=m+p＞0, m＞0, p＞0, i 〉=0.
7. according to claim 3ly contain two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, it is characterized in that: the catalyzer addition of described Stille coupling reaction is 0.05%～50% of a compd A molar percentage.
8. according to claim 7ly contain two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, it is characterized in that: described catalyzer is the mixture of organic palladium catalyzer or organic palladium catalyzer and organophosphorus ligand;
Described organic palladium catalyzer is Pd
2(dba)
3, Pd (PPh
3)
4, Pd (PPh
3)
2Cl
2In at least a; Described organophosphorus ligand is P (o-Tol)
3
The organic solvent of described Stille coupling reaction is at least a in tetrahydrofuran (THF), glycol dimethyl ether, benzene, chlorobenzene, the toluene.
9. according to claim 3ly contain two thiophene thiophenes and cough up-thiophene-quinoxaline method for preparing conjugated polymer, it is characterized in that: the temperature of described Stille coupling reaction is 50～150 ℃, and the time is 24～72 hours.
10. each describedly contains two thiophene thiophenes and coughs up according to claim 1 to 2-thiophene-quinoxaline conjugated polymers at organic photoelectrical material, polymer solar battery, organic electroluminescence device, organic field effect tube, organic light storage device or/and the application in the organic laser apparatus.
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| EP2813526A4 (en) * | 2012-02-06 | 2015-09-16 | Lg Chemical Ltd | Polymer and organic solar cell including same |
| CN113831511A (en) * | 2021-09-08 | 2021-12-24 | 南方科技大学 | Polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline and preparation method and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2813526A4 (en) * | 2012-02-06 | 2015-09-16 | Lg Chemical Ltd | Polymer and organic solar cell including same |
| US9184392B2 (en) | 2012-02-06 | 2015-11-10 | Lg Chem, Ltd. | Polymer and organic solar cell including same |
| CN103833985A (en) * | 2012-11-27 | 2014-06-04 | 海洋王照明科技股份有限公司 | [3,2-b]bi-thiofuran-benzo-2(benzo-selenium diazole) combined copolymer as well as preparation method and application thereof |
| CN103833985B (en) * | 2012-11-27 | 2016-02-10 | 海洋王照明科技股份有限公司 | And [3,2-b] two thiophene-benzo two (selenole) multipolymer and its preparation method and application |
| CN113831511A (en) * | 2021-09-08 | 2021-12-24 | 南方科技大学 | Polymer containing dithiophene [3,2-f:2',3' -h ] quinoxaline and preparation method and application thereof |
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