CN102311537B - Polymer containing fluorine, anthracene and 2-thienyl thienopyrazine unit as well as preparation method and application thereof - Google Patents
Polymer containing fluorine, anthracene and 2-thienyl thienopyrazine unit as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a polymer containing a fluorine, anthracene and 2-thienyl thienopyrazine unit, which has the structure disclosed in the specification, wherein n is an integer from 1 to 100, and m is an integer from 6 to 20; x and y are positive real numbers, and x + y = 1; R1 and R2 are H, F, cyan, alkyl of C1-C18 and alkoxy of C1-C18; R3 is H, phenyl, alkyl of C1-C12, aromatic alkyl of C6-40 and aryl alkoxy of C6-C40. The polymer containing the fluorine, anthracene and 2-thienyl thienopyrazine unit has a lower energy gap, higher mobility, a wide range of spectral absorption and wide application prospects in the photoelectricity field. The invention also provides a preparation method of the polymer containing the fluorene, anthracene and 2-thienyl thienopyrazine unit.
Description
[technical field]
The present invention relates to the material technology field, relate in particular to a kind of polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit and its preparation method and application.
[background technology]
Traditional high efficiency solar cell is mainly take inorganic semiconductor silicon as raw material, but the silicon wafer solar cell consumes energy greatly because production process technology is complicated, seriously polluted, and cost is high, has suppressed the development of its commercial applications.Therefore utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Organic semiconductor material is on the one hand because the environmental stability of organic materials is good, preparation cost is low, function is easy to modulation, snappiness and film-forming properties are all better; On the other hand because the organic solar batteries course of processing is relatively simple, but cold operation, and the element manufacturing cost is the advantage such as lower and receiving much concern also, becomes cheap and attractive solar cell material.In addition, but organic solar batteries also have the big area manufacturing, can use the advantages such as flexible substrate, environmental friendliness, light portable.
The organic photovoltaic material has following advantage: Heat stability is good, and easily processing, cost is low, can realize specific photoelectric functional by molecular designing.Anthracene and derivative thereof have good stability and film-forming properties preferably; Its uv-vis spectra presents wider finger peak and absorbs, and is conducive to improve sun Optical Absorption coverage; And it has suitable carrier transmission characteristics, and hole mobility can reach 3cm under its crystal room temperature
2/ Vs is the organic semiconductor material of a class excellence.Although anthracene and derivative thereof are existing a lot of as the report of electroluminescent organic material, rarely have report as the research of organic photovoltaic material, this has just limited its range of application greatly.
[summary of the invention]
Based on this, be necessary to provide a kind of organic photovoltaic compound that contains fluorenes, anthracene and dithienyl thienopyrazine unit.
In addition, also be necessary to provide a kind of preparation method of the organic photovoltaic compound that contains fluorenes, anthracene and dithienyl thienopyrazine unit and point out that it is in the application of photoelectric field.
A kind of polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit has following structure:
Wherein, n is 1～100 integer, and m is 6～20 integer; X, y are arithmetic number, and x+y=1; R
1, R
2Be H, F, cyano group, C
1～C
18Alkyl, C
1～C
18Alkoxyl group; R
3Be H, phenyl, C
1～C
12Alkyl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
A kind of preparation method who contains the polymkeric substance of fluorenes, anthracene and dithienyl thienopyrazine unit comprises the steps:
S11, the compd A 1, A2, the A3 that provide following structural formula to represent respectively:
Wherein, m is 6～20 integer;
S12, in oxygen-free environment, under organic solvent, catalyzer and the alkaline solution existence condition, compd A 1, A2, A3 are carried out the Suzuki coupled reaction, obtain the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit that following structural formula represents:
Wherein, n is 1～100 integer, and m is 6～20 integer; X, y are arithmetic number, and x+y=1; R
1, R
2Be H, F, cyano group, C
1～C
18Alkyl, C
1～C
18Alkoxyl group; R
3Be H, phenyl, C
1～C
12Alkyl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
Preferably, the compd A among the step S11 1 is made by following steps:
Compound D and the E of following structural formula are provided respectively:
Wherein, m is 1～20 integer;
In the anhydrous and oxygen-free environment, under-70 ℃～-85 ℃ conditions, Compound D being added in the solvent, is to add mixing behind the n-Butyl Lithium in 2: 1～4: 1 by n-Butyl Lithium and Compound D mol ratio; Described solvent is one or more that are selected from tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane and the ethyl acetate;
2～4 times by the Compound D mole number add compd E, are warming up to room temperature reaction 12～48 hours, obtain the compd A 1 of following structural formula:
Preferably, among the step S12, organic solvent is one or more that are selected from toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane and the ethyl acetate; Catalyzer is Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2Cl
2Alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; The catalyzer add-on is 0.5%～20% of described compd A 1 mole number; The add-on of described alkaline solution is 5～10 times of described compd A 1 mole number; In the Suzuki coupled reaction, temperature of reaction is 60～120 ℃, and the reaction times is 12～72 hours.
Preferably, above-mentioned preparation method also comprises the purge process that makes behind the polymkeric substance, and concrete steps are as follows:
Add deionized water in the polymkeric substance that makes to step S12 and toluene extracts, get organic phase, splash in the anhydrous methanol after with the organic phase distillation with the method for underpressure distillation and constantly to stir, separate out solid precipitation, through obtaining pressed powder after suction filtration, the oven dry, again pressed powder is dissolved with chloroform, cross the neutral alumina chromatography column and separate, revolve steaming after removing catalyzer, splash into again in the methanol solvate and stir, use at last the Soxhlet extractor extracting, obtain the polymkeric substance behind the purifying.
A kind of solar cell device of above-mentioned polymkeric substance preparation, comprise substrate, be deposited on one of substrate lip-deep, as the conductive layer of anode, be coated in and play poly-3 of modification on the conductive layer, 4-Ethylenedioxy Thiophene: polystyrolsulfon acid layer, be coated in poly-3,4-Ethylenedioxy Thiophene: the active coating on polystyrolsulfon acid layer surface, and be arranged on the active coating surface, as the metal aluminium lamination of negative electrode; The material of active coating is mixture, comprises electron donor material and electron acceptor material; Electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate, electron donor material contain the above-mentioned polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit.
A kind of organic electroluminescence device of above-mentioned polymkeric substance preparation, comprise substrate, be deposited on of substrate lip-deep, as the conductive layer of anode, be coated in the luminescent layer on the conductive layer, be coated in the buffer layer take LiF as material on the luminescent layer, and be arranged on the buffer layer, as the metal aluminium lamination of negative electrode, the luminescent layer material contains the above-mentioned polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit.
A kind of organic field effect tube of above-mentioned polymkeric substance preparation, its structure comprises successively: doped silicon wafer, SiO
2Insulation layer is used for modifying SiO
2The octadecyl trichlorosilane alkane layer of insulation layer, be coated in the organic semiconductor layer on the octadecyl trichlorosilane alkane layer, be disposed on source electrode and drain electrode on the organic semiconductor layer, the organic semiconductor layer material contains the above-mentioned polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit.
Anthracene and derivative thereof have good stability and film-forming properties preferably; Its uv-vis spectra presents wider finger peak and absorbs, and is conducive to improve sun Optical Absorption coverage; And it has suitable carrier transmission characteristics, and hole mobility can reach 3cm under its crystal room temperature
2/ Vs is the organic semiconductor material of a class excellence.The compound that contains the fluorenes unit has the structure of easy modification, has good photo and thermal stability and film-forming properties.
This polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit has lower energy gap, higher mobility, and the absorption region of spectrum is wide, and this polymer materials is conducive to current carrier and more effectively transmits in active layer material inside.
[description of drawings]
Fig. 1 is the structural representation of an embodiment of solar cell device;
Fig. 2 is the structural representation of an embodiment of organic electroluminescence device;
Fig. 3 is the structural representation of an embodiment of organic field effect tube.
[embodiment]
A kind of polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit and preparation method thereof is provided, and has pointed out the application of this polymer materials at photoelectric field.
A kind of polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit has following structure:
Wherein, n is 1～100 integer, and m is 6～20 integer; X, y are arithmetic number, and x+y=1; R
1, R
2Be H, F, cyano group, C
1～C
18Alkyl, C
1～C
18Alkoxyl group; R
3Be H, phenyl, C
1～C
12Alkyl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
A kind of preparation method who contains the polymkeric substance of fluorenes, anthracene and dithienyl thienopyrazine unit, step is as follows:
Step 1
Compound D and the E of following structural formula are provided respectively:
Wherein, m is 1～20 integer;
In the anhydrous and oxygen-free environment, under-70 ℃～-85 ℃ conditions, Compound D being added in the solvent, is to add mixing behind the n-Butyl Lithium in 2: 1～4: 1 by n-Butyl Lithium and Compound D mol ratio; Described solvent is one or more that are selected from tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane and the ethyl acetate;
2～4 times by the Compound D mole number add compd E, are warming up to room temperature reaction 12～48 hours, obtain the compd A 1 of following structural formula:
Step 2
The compd A 1, A2, the A3 that provide following structural formula to represent:
A3: dithienyl thiophene [3,4-b] and pyrazine or derivatives thereof; Wherein, m is 6～20 integer;
In oxygen-free environment, under organic solvent, catalyzer and the alkaline solution existence condition, compd A 1, A2, A3 are carried out the Suzuki coupled reaction, obtain the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit that following structural formula represents:
Wherein, n is 1～100 integer, and m is 6～20 integer; X, y are arithmetic number, and x+y=1; R
1, R
2Be H, F, cyano group, C
1～C
18Alkyl, C
1～C
18Alkoxyl group; R
3Be H, phenyl, C
1～C
12Alkyl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
Preferably, in the step 2, organic solvent is one or more that are selected from toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane and the ethyl acetate; The catalyzer add-on is 0.5%～20% of compd A 1 mole number; Catalyzer is Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2Cl
2The alkaline solution add-on is 5～10 times of described compd A 1 mole number; Alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution; Suzuki reaction response temperature is 60～120 ℃, and the reaction times is 12～72 hours.
In concrete embodiment, above-mentioned oxygen free condition can be realized by the mode of nitrogen or protection of inert gas; The numerical value of x, y depends on compd A 1, A2, A3 three's feed ratio in the polymkeric substance.
Step 3
Add deionized water in the above-mentioned polymkeric substance that makes and toluene extracts, get organic phase, it is splashed in the anhydrous methanol after with the organic phase distillation with the method for underpressure distillation and constantly to stir, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry, again pressed powder is dissolved with chloroform, cross the neutral alumina chromatography column, revolve steaming after removing catalyzer, again it is splashed in the methanol solvate and stir, use at last the Soxhlet extractor extracting, obtain the polymkeric substance behind the purifying.
Below in conjunction with specific embodiment above-mentioned polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit and its preparation method and application is further described.
Embodiment 1
Open following polymer P 1, the P2 of structure of present embodiment
P1?x＝0.1，y＝0.9
P2?x＝0.5，y＝0.5
Preparation process is as follows:
One, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under, add 2 of white in the there-necked flask, 7-two bromo-9,9-dioctyl fluorene 9.0mmol injects the refining tetrahydrofuran solvent of 150ml with syringe, slowly injects 27.0mmol n-BuLi, stirring reaction with syringe again under-78 ℃ of conditions.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, behind the suction filtration with filtrate collection and revolve and evaporate solvent.At last with the crude product sherwood oil: (v/v=15: 1) separate for leacheate carries out silica gel column chromatography, obtain pulverulent solids 2,7-two (4,4 for ethyl acetate, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene, productive rate 65%.GC-MS(EI-m/z)：642(M
+)。
Two, the preparation of polymer P 1, P2
P1?x＝0.1，y＝0.9
P2?x＝0.5，y＝0.5
The preparation of P1
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.1mmol, 5, the Na of 7-two (5 '-bromothiophene base) thiophene [3,4-b] and pyrazine 0.9mmol, tetra-triphenylphosphine palladium 0.025mmol, 2mol/L
2CO
3Aqueous solution 5ml and toluene solvant 30ml are by repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, under 80 ℃ of conditions, react 72h.
Behind the reaction 72h, add deionized water in the reaction flask of product and toluene extracts, get organic phase, with the method for underpressure distillation with polymkeric substance/toluene solution evaporate to dryness to about 5ml, it is splashed into constantly stirring in the 300ml anhydrous methanol, and have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 1 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 1 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 71100, the polymkeric substance monodispersity is that 2.38, n is 11.
The preparation of P2
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-dibromoanthracene 0.5mmol, 5,7-two (5 '-bromothiophene base) thiophene [3,4-b] and pyrazine 0.5mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 2.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 2 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 125000, the polymkeric substance monodispersity is that 2.66, n is 100.
Embodiment 2
Open following polymer P 3, the P4 of structure of present embodiment
P3?x＝0.8，y＝0.2
P4?x＝0.2，y＝0.8
Preparation process is as follows:
One, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under, add 2 of white in the there-necked flask, 7-two bromo-9,9-dioctyl fluorene 9.0mmol injects the refining tetrahydrofuran solvent of 150ml with syringe, slowly injects 27.0mmol n-BuLi, stirring reaction with syringe again under-78 ℃ of conditions.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, behind the suction filtration with filtrate collection and revolve and evaporate solvent.At last with the crude product sherwood oil: (v/v=15: 1) separate for leacheate carries out silica gel column chromatography, obtain pulverulent solids 2,7-two (4,4 for ethyl acetate, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene, productive rate 65%.GC-MS(EI-m/z)：642(M
+)。
Two, the preparation of polymer P 3, P4
P3?x＝0.8，y＝0.2
P4?x＝0.2，y＝0.8
The preparation of P3
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2, and 6-two (2-octyl-decyl) anthracene 0.8mmol (this compou nd synthesis method is referring to Macromol.Chem.Phys.2006, and 207,1107-1115), 5,7-two (5 '-bromothiophene base)-2, (this compou nd synthesis method is referring to Adv.Mater.2010 for 3-diphenyl thiophene [3,4-b] and pyrazine 0.2mmol, 22, E1-E17), the Na of tetra-triphenylphosphine palladium 0.02mmol, 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 40ml are by repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, under 100 ℃ of conditions, react 12h.
Behind the reaction 12h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 3 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 3 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 98200, the polymkeric substance monodispersity is that 2.87, n is 20.
The preparation of P4
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2,6-two (2-octyl-decyl) anthracene 0.2mmol, 5,7-two (5 '-bromothiophene base)-2,3-diphenyl thiophene [3,4-b] and pyrazine 0.8mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 4.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 4 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 76200, the polymkeric substance monodispersity is that 2.41, n is 17.
Embodiment 3
Open following polymer P 5, the P6 of structure of present embodiment
P5?x＝0.5，y＝0.5
P6?x＝0.6，y＝0.4
Preparation process is as follows:
One, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under, add 2 of white in the there-necked flask, 7-two bromo-9,9-dioctyl fluorene 9.0mmol injects the refining tetrahydrofuran solvent of 150ml with syringe, slowly injects 27.0mmol n-BuLi, stirring reaction with syringe again under-78 ℃ of conditions.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, behind the suction filtration with filtrate collection and revolve and evaporate solvent.At last with the crude product sherwood oil: (v/v=15: 1) separate for leacheate carries out silica gel column chromatography, obtain pulverulent solids 2,7-two (4,4 for ethyl acetate, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene, productive rate 65%.GC-MS(EI-m/z)：642(M
+)。
Two, the preparation of polymer P 5, P6
P5?x＝0.5，y＝0.5
P6?x＝0.6，y＝0.4
The preparation of P5
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9, (synthetic method of this compound is referring to J.Org.Chem. for 10-two bromo-2-fluorine anthracene 0.5mmol, 2003,68,216-226), 5,7-two (5 '-bromothiophene base)-2, (this compou nd synthesis method is referring to Solar Energy Materials﹠amp for 3-two (to octyl phenyl) thiophene [3,4-b] and pyrazine 0.5mmol; Solar Cells 91, (2007), 1010-1018), Pd (PPh
3)
2Cl
20.02mmol, the Na of 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 40ml are by repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, under 120 ℃ of conditions, react 58h.
Behind the reaction 58h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 5 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 5 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 118200, the polymkeric substance monodispersity is that 2.53, n is 72.
The preparation of P6
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-2-fluorine anthracene 0.6mmol, 5,7-two (5 '-bromothiophene base)-2,3-two (to octyl phenyl) thiophene [3,4-b] and pyrazine 0.4mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 6.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 6 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 61400, the polymkeric substance monodispersity is that 2.36, n is 16.
Embodiment 4
Open following polymer P 7, the P8 of structure of present embodiment
P7?x＝0.5，y＝0.5
P8?x＝0.4，y＝0.6
Preparation process is as follows:
One, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9, the preparation of 9-dioctyl fluorene
Put up the anhydrous and oxygen-free reaction unit, constantly stirring and N
2Protection under, add 2 of white in the there-necked flask, 7-two bromo-9,9-dioctyl fluorene 9.0mmol injects the refining tetrahydrofuran solvent of 150ml with syringe, slowly injects 27.0mmol n-BuLi, stirring reaction with syringe again under-78 ℃ of conditions.React after 2 hours, under-78 ℃ of conditions, inject 30.6mmol 2-isopropoxy-4,4,5 with syringe, 5-tetramethyl--1,3,2-two assorted oxygen pentaboranes are warmed up to room temperature reaction and spend the night.
After reaction finishes, add the saturated NaCl aqueous solution, chloroform extraction, anhydrous sodium sulfate drying, behind the suction filtration with filtrate collection and revolve and evaporate solvent.At last with the crude product sherwood oil: (v/v=15: 1) separate for leacheate carries out silica gel column chromatography, obtain pulverulent solids 2,7-two (4,4 for ethyl acetate, 5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene, productive rate 65%.GC-MS(EI-m/z)：642(M
+)。
Two, the preparation of polymer P 7, P8
P7?x＝0.5，y＝0.5
P8?x＝0.4，y＝0.6
The preparation of P7
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-1, (synthetic method of this compound is referring to J.Org.Chem. for 4-dimethoxy anthracene 0.5mmol, 2006,71,1795-1801), 5,7-two (5 '-bromothiophene base)-2,3-two (to 2-ethyl hexyl oxy phenyl) thiophene [3,4-b] and pyrazine 0.5mmol (this compou nd synthesis method is referring to Adv.Mater., and 2006,18,2169-2173), Pd
2(dba)
3/ P (o-Tol)
30.02mmol, the Na of 2mol/L
2CO
3Aqueous solution 10ml and toluene solvant 50ml are by repeatedly leading to N
2Make reaction system be in anaerobic state with vacuumizing, under 95 ℃ of conditions, react 64h.
Behind the reaction 64h, adding deionized water and toluene extract in the reaction flask, get organic phase, method with underpressure distillation is extremely a small amount of with polymkeric substance/toluene solution evaporate to dryness, it is splashed into constantly stirring in the 300ml anhydrous methanol, have solid precipitation to separate out, through obtaining pressed powder after suction filtration, the oven dry.Again pressed powder is dissolved with chloroform, cross chromatography column with neutral alumina, remove catalyzer, polymkeric substance/chloroformic solution is revolved steam to the surplus 5ml at last, splash into it in methanol solvate and stirred for several hour, at last polymer P 7 is collected oven dry.With Soxhlet extractor with the polymkeric substance extracting, thereby improve the monodispersity of polymericular weight.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 7 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 98400, the polymkeric substance monodispersity is that 2.93, n is 57.
The preparation of P8
In reactor, add 2,7-two (4,4,5,5-tetramethyl--1,3,2-two assorted oxygen pentaboranes) base-9,9-dioctyl fluorene 1mmol, 9,10-two bromo-1,4-dimethoxy anthracene 0.4mmol, 5,7-two (5 '-bromothiophene base)-2,3-two (to 2-ethyl hexyl oxy phenyl) thiophene [3,4-b] and pyrazine 0.6mmol, other object charging capacity, reaction conditions and post-treating method are all constant, then finally obtain polymer P 8.
Adopt Waters Breeze gel chromatograph, the tetrahydrofuran (THF) that polymer P 8 after purifying is dissolved in after making with extra care is made into 1mg/1mL solution, filter behind the insolubles with 10 microliter amount with the supporting filter membrane of instrument, the sample introduction speed of 1ml/min is carried out the GPC test, number-average molecular weight Mn ≈ 74400, the polymkeric substance monodispersity is that 2.11, n is 16.
Following examples are to contain the polymkeric substance of fluorenes, anthracene and dithienyl thienopyrazine unit at polymer solar battery, organic electroluminescence device, organic field effect tube, organic optical storage, the application in the fields such as organic non-linear optical properties and organic laser material.
Embodiment 5
A kind of solar cell device, its structure such as Fig. 1.Adopt ito glass (indium tin oxide glass) in the present embodiment, namely glass is as substrate, and ITO (indium tin oxide) is as conductive layer, and polymkeric substance adopts the polymer P 1 in the previous embodiment 1.
The structure of this solar cell device is: glass/ITO/PEDOT:PSS/ active coating/Al; Wherein, the material of active coating is mixture, comprises with [6,6] phenyl-C
61-methyl-butyrate is electron donor material and the electron acceptor material take the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit as material of material; ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-3,4-Ethylenedioxy Thiophene, and PSS is polystyrolsulfon acid.
The manufacturing processed of this solar cell device is as follows:
Ito glass process ultrasonic cleaning, and with after oxygen-Plasma processing, be coated with the PEDOT:PSS layer that last layer plays modification on the ITO surface;
Adopt spin coating technique to apply one deck active coating at described PEDOT:PSS layer, the material of this active coating comprises with [6,6] phenyl-C
61-methyl-butyrate is electron donor material and the electron acceptor material take the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit as material of material;
At the surface vacuum evaporation metal aluminium of described active coating, form the metal aluminium lamination as negative electrode, obtain described organic solar batteries device.In the present embodiment, the thickness of metal aluminium lamination is respectively 170nm, and in other embodiment, the thickness of metal aluminium lamination can also be 30nm, 130nm, 60nm.
In the present embodiment, after this used for solar batteries epoxy encapsulation, through annealing under 110 degrees centigrade of air tight conditions 2 hours, drop to again room temperature, the chemical structure of the annealed rear material of device is more regular, has improved transmission speed and the efficient of current carrier, and then improves photoelectric transformation efficiency.
Embodiment 6
A kind of organic electroluminescence device, structure are as shown in Figure 2.Adopt ito glass (indium tin oxide glass) in the present embodiment, namely glass is as substrate, and ITO (indium tin oxide) is as conductive layer, and polymkeric substance adopts the polymer P 1 in the previous embodiment 1.
The structure of this organic electroluminescence device is: glass/ITO/ luminescent layer/buffer layer/Al; Wherein, luminescent layer adopts the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit; The buffer layer material is LiF; ITO is that square resistance is the tin indium oxide of 10-20 Ω/mouth, and PEDOT is poly-3,4-Ethylenedioxy Thiophene, and PSS is polystyrolsulfon acid.
The manufacturing processed of this organic electroluminescence device is as follows:
Ito glass process ultrasonic cleaning, and with after oxygen-Plasma processing, be coated with the polymer formation luminescent layer that last layer contains fluorenes, anthracene and dithienyl thienopyrazine unit on the ITO surface;
Described luminous on vacuum evaporation LiF form buffer layer;
At the surface vacuum evaporation metal aluminium of described buffer layer, form the metal aluminium lamination as negative electrode, obtain described organic electroluminescence device.
The ITO layer is as anode in the present embodiment.
Embodiment 7
A kind of organic field effect tube, structure are as shown in Figure 3.Adopt highly doped silicon chip as substrate in the present embodiment, polymkeric substance adopts the polymer P 1 in the previous embodiment 1.
The structure of this organic field effect tube is: Si/SiO
2/ OTS/ organic semiconductor layer/source electrode (S) and drain electrode (D); Wherein, SiO
2Thickness is 450nm, plays insulating effect; OTS is octadecyl trichlorosilane alkane; The organic semiconductor layer material is the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit; Source electrode (S) and drain electrode (D) adopt metallic gold to make, and in other embodiment, source electrode (S) and drain electrode (D) also can adopt metallic copper to make.
The manufacturing processed of this organic field effect tube is as follows:
Clean doped silicon substrate, deposition has the SiO of insulating effect
2Layer;
At described SiO
2Apply OTS on the insulation layer, form the OTS layer;
Apply the polymkeric substance that one deck contains fluorenes, anthracene and dithienyl thienopyrazine unit at described OTS layer, form organic semiconductor layer;
At described organic semiconductor layer source electrode and the drain electrode of metallic gold material are set, obtain described organic field effect tube.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to claim of the present invention.Should be pointed out that for the person of ordinary skill of the art without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (7)
1. polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit has following structure:
Wherein, n is 1～100 integer, and m is 6～20 integer;
X, y are arithmetic number, and x+y=1;
R
1, R
2Be H, F, cyano group, C
1～C
18Alkyl, C
1～C
18Alkoxyl group;
R
3Be H, phenyl, C
1～C
12Alkyl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl.
2. a preparation method who contains the polymkeric substance of fluorenes, anthracene and dithienyl thienopyrazine unit is characterized in that, comprises the steps:
S11, the compd A 1, A2, the A3 that provide following structural formula to represent respectively:
Wherein, m is 6～20 integer;
S12, in oxygen-free environment, under organic solvent, catalyzer and the alkaline solution existence condition, compd A 1, A2, A3 are carried out the Suzuki coupled reaction, obtain the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit that following structural formula represents:
Wherein, n is 1～100 integer, and m is 6～20 integer;
X, y are arithmetic number, and x+y=1;
R
1, R
2Be H, F, cyano group, C
1～C
18Alkyl, C
1～C
18Alkoxyl group;
R
3Be H, phenyl, C
1～C
12Alkyl, C
6～C
40Aralkyl, C
6～C
40Alkoxy aryl;
Described organic solvent is one or more that are selected from toluene, glycol dimethyl ether, tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane and the ethyl acetate;
Described catalyzer is Pd (PPh
3)
4, Pd
2(dba)
3/ P (o-Tol)
3Or Pd (PPh
3)
2Cl
2
Described alkaline solution is the NaOH aqueous solution, Na
2CO
3The aqueous solution, NaHCO
3The aqueous solution or the tetraethyl ammonium hydroxide aqueous solution;
Described catalyzer add-on is 0.5%～20% of described compd A 1 mole number;
The add-on of described alkaline solution is 5～10 times of described compd A 1 mole number;
In the described Suzuki coupled reaction, temperature of reaction is 60～120 ℃, and the reaction times is 12～72 hours.
3. preparation method as claimed in claim 2 is characterized in that, among the step S11, described compd A 1 is made by following steps:
Compound D and the E of following structural formula are provided respectively:
Wherein, m is 6～20 integer;
In the anhydrous and oxygen-free environment, under-70 ℃～-85 ℃ conditions, Compound D being added in the solvent, is 2: 1～4: 1 adding n-Butyl Lithiums by n-Butyl Lithium and Compound D mol ratio, stirs 2 hours; Wherein, described solvent is one or more that are selected from tetrahydrofuran (THF), ether, methylene dichloride, trichloromethane and the ethyl acetate;
2～4 times by the Compound D mole number add compd E, are warming up to room temperature reaction 12～48 hours, obtain the compd A 1 of following structural formula:
4. preparation method as claimed in claim 2 is characterized in that, also comprises the purge process that makes behind the polymkeric substance, and concrete steps are as follows:
Add deionized water in the polymkeric substance that makes to step S12 and toluene extracts, get organic phase, splash in the anhydrous methanol after with the organic phase distillation with the method for underpressure distillation and constantly to stir, separate out solid precipitation, through obtaining pressed powder after suction filtration, the oven dry, again pressed powder is dissolved with chloroform, cross the neutral alumina chromatography column and separate, revolve steaming after removing catalyzer, splash into again in the methanol solvate and stir, use at last the Soxhlet extractor extracting, obtain the polymkeric substance behind the purifying.
5. the solar cell device of the described polymkeric substance preparation of a claim 1, comprise substrate, be deposited on one of described substrate lip-deep, as the conductive layer of anode, be coated in and play poly-3 of modification on the described conductive layer, 4-Ethylenedioxy Thiophene: polystyrolsulfon acid layer, be coated in described poly-3,4-Ethylenedioxy Thiophene: the active coating on polystyrolsulfon acid layer surface, and be arranged on described active coating surface, as the metal aluminium lamination of negative electrode; The material of described active coating is mixture, comprises electron donor material and electron acceptor material; Described electron acceptor material is [6,6] phenyl-C
61-methyl-butyrate is characterized in that, described electron donor material contains the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit claimed in claim 1.
6. the organic electroluminescence device of the described polymkeric substance preparation of a claim 1, comprise substrate, be deposited on of described substrate lip-deep, as the conductive layer of anode, be coated in the luminescent layer on the described conductive layer, be coated in the buffer layer take LiF as material on the described luminescent layer, and be arranged on the described buffer layer, as the metal aluminium lamination of negative electrode, it is characterized in that described luminescent layer material contains the polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit claimed in claim 1.
7. the organic field effect tube of the described polymkeric substance preparation of a claim 1, its structure comprises successively: doped silicon wafer, SiO
2Insulation layer is used for modifying described SiO
2The octadecyl trichlorosilane alkane layer of insulation layer, be coated in the organic semiconductor layer on the described octadecyl trichlorosilane alkane layer, be disposed on source electrode and drain electrode on the described organic semiconductor layer, it is characterized in that the with dividend right profit of described organic semiconductor layer material requires the 1 described polymkeric substance that contains fluorenes, anthracene and dithienyl thienopyrazine unit.
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| US6413658B1 (en) * | 1999-07-06 | 2002-07-02 | Fuji Photo Film Co., Ltd. | Polymers, luminescent device materials, and luminescent devices comprising said materials |
| CN101133098A (en) * | 2005-03-04 | 2008-02-27 | 住友化学株式会社 | Biscarbazol-9-yl-substituted triarylamine-containing polymers and electronic devices |
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| CN101133098A (en) * | 2005-03-04 | 2008-02-27 | 住友化学株式会社 | Biscarbazol-9-yl-substituted triarylamine-containing polymers and electronic devices |
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