CN103012749A - Difluoro-benzo-triazole-based copolymer containing carbazole unit, preparation method thereof and application thereof - Google Patents

Difluoro-benzo-triazole-based copolymer containing carbazole unit, preparation method thereof and application thereof Download PDF

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CN103012749A
CN103012749A CN201110286591XA CN201110286591A CN103012749A CN 103012749 A CN103012749 A CN 103012749A CN 201110286591X A CN201110286591X A CN 201110286591XA CN 201110286591 A CN201110286591 A CN 201110286591A CN 103012749 A CN103012749 A CN 103012749A
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multipolymer
difluoride
triazolyl
carbazole unit
compd
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周明杰
王平
张振华
梁禄生
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Oceans King Lighting Science and Technology Co Ltd
Shenzhen Oceans King Lighting Engineering Co Ltd
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Abstract

The invention belongs to the field of solar cells, and discloses a difluoro-benzo-triazole-based copolymer containing a carbazole unit, a preparation method thereof and an application thereof. The copolymer has a following structural of formula (I) as shown in the specification, wherein in the formula, R1 and R2 are all C1 to C20 alkyl, and n is an integer from 10 to 100. According to the difluoro-benzo-triazole-based copolymer containing the carbazole unit, 1,2,3-benzotriazole polymer contains two fluorine atoms and an HOMO energy level of the polymer is reduced by 0.1 eV, fluorine-substituted 1,2,3-benzotriazole has two imino groups with strong electron withdrawing and is a heterocyclic compound with a strong electron-withdrawing property, and an N atom on an N-H bond of the benzotriazole is easy to be introduced with an alkyl chain, wherein functional groups of the alkyl chain can improve energy conversion efficiency of solar energy, thereby solving problems of low efficiency of the polymer solar cells.

Description

Contain carbazole unit phenyl-difluoride and triazolyl multipolymer and its preparation method and application
Technical field
The present invention relates to the solar cell material field, relate in particular to a kind of carbazole unit phenyl-difluoride and triazolyl multipolymer and its preparation method and application of containing.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.Be used at present the silicon wafer battery on ground owing to complex manufacturing, cost are high, its application is restricted.In order to reduce the battery cost, expand range of application, people are seeking novel solar cell material always for a long time.Organic semiconductor material with its raw material be easy to get, cheap, preparation technology is simple, environmental stability good, have the good advantages such as photovoltaic effect to receive much concern.From N.S.Sariciftci in 1992 etc. at SCIENCE (N.S Sariciftci, L.Smilowitz, A.J.Heeger, et al.Science, 1992,258,1474) upper report conjugated polymers and C 60Between the Photoinduced Electron transfer phenomena after, people have dropped into large quantity research aspect polymer solar battery, and have obtained development at full speed, but still much lower than the efficiency of conversion of inorganic solar cell.
Summary of the invention
Purpose one of the present invention be to provide a kind of effciency of energy transfer high contain carbazole unit phenyl-difluoride and triazolyl multipolymer.
A kind of have a following structural formula (I) contain carbazole unit phenyl-difluoride and triazolyl multipolymer:
In the formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer, preferred n is 50～70.
Another object of the present invention is to provide the above-mentioned preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer, comprise the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
Figure BDA0000093965260000021
Wherein, in the described compd A, R 1Be C 1～C 20Alkyl; In the described compd B, R 2Be C 1～C 20Alkyl;
S2, under oxygen-free environment, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer and alkaline solution, in carrying out the Suzuki coupling reaction under 70～130 ℃ after 12～96 hours, obtain having following structural formula described carbazole unit phenyl-difluoride and the triazolyl multipolymer of containing of (I):
Figure BDA0000093965260000022
In the formula, n is the integer of 10-100.
The above-mentioned preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer also comprises the steps:
S3, describedly contain the carbazole unit phenyl-difluoride and the triazolyl multipolymer carries out purification process to what make among the step S2.
In the above-mentioned preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer, among the described step S2:
Described catalyzer is organic palladium, or the mixture of organic palladium and organophosphor ligand; The mol ratio of described organic palladium and described compd A is 1: 20～1: 100.
Described organic solvent is selected from least a in toluene, DMF and the tetrahydrofuran (THF);
Described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and the sodium hydrogen carbonate solution.
Preferably, among the described step S2:
The preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer, described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
Another purpose of the present invention is to provide above-mentioned contain carbazole unit phenyl-difluoride and the application of triazolyl multipolymer in the organic solar batteries active coating.
Carbazole unit phenyl-difluoride and the triazolyl multipolymer of containing provided by the invention, because 1,2,3-benzotriazole polymkeric substance contains two fluorine atoms, its HOMO energy level will reduce 0.11eV, and fluorine replaces 1,2, the 3-benzotriazole has again two strong electrophilic imido grpups, 1,2 of fluorine replacement, the 3-benzotriazole is a heterogeneous ring compound that strong electrophilic performance is arranged, and the upper alkyl chain of introducing easily of the N of the N-H key of benzotriazole, this alkyl chain functional groups can improve the effciency of energy transfer of sun power, thereby solves the polymer solar battery low efficiency problem.
Description of drawings
Fig. 1 is preparation technology's schema that the present invention contains fluorenes phenyl-difluoride and triazolyl multipolymer;
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of the multipolymer of embodiment 1 preparation;
Fig. 3 is the organic solar energy cell structure synoptic diagram of embodiment 6.
Embodiment
Provided by the invention have a following structural formula (I) contain carbazole unit phenyl-difluoride and triazolyl multipolymer:
Figure BDA0000093965260000041
In the formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer; N is preferably 50～70.
The above-mentioned preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer as shown in Figure 1, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
Figure BDA0000093965260000042
Namely 2,7-hypoboric acid pinacol ester-9-alkyl carbazole;
Figure BDA0000093965260000043
Be 2-alkyl-4,7-two (5-bromothiophene base)-5,6-two fluoro-1,2,3-benzotriazole;
Wherein, in the compd A, R 1Be C 1～C 20Alkyl; In the compd B, R 2Be C 1～C 20Alkyl;
S2, oxygen-free environment (as, the oxygen-free environment that nitrogen, argon gas or nitrogen and argon gas gas mixture etc. consist of) under, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer and alkaline solution, in carrying out the Suzuki coupling reaction under 70～130 ℃ after 12～96 hours, obtain reaction solution, comprise product in this reaction solution, namely have described carbazole unit phenyl-difluoride and the triazolyl multipolymer of containing of following structural formula (I):
Figure BDA0000093965260000051
In the formula, n is 10～100 integer;
S3, the product among the step S2 is carried out purification process:
In the reaction solution of step S2, add methyl alcohol, carry out precipitating and process, filter with apparatus,Soxhlet's subsequently, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourlessly as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, behind 50 ℃ of dry 24h under the vacuum, what obtain purifying contains carbazole unit phenyl-difluoride and triazolyl multipolymer with red powder.
In the above-mentioned preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer, among the described step S2:
Described catalyzer is organic palladium, as, bi triphenyl phosphine dichloride palladium, three dibenzalacetones, two palladiums or tetra-triphenylphosphine palladium; Described catalyzer also can be the mixture of organic palladium and organophosphor ligand, as, the mixture of three dibenzalacetones, two palladiums and tri-butyl phosphine; The mol ratio of described organic palladium and described compd A is 1: 20～1: 100; In the mixture of organic palladium and organophosphor ligand, the mol ratio of organic palladium and organophosphor ligand is 1: 3～1: 6.
Described organic solvent is selected from least a in toluene, DMF and the tetrahydrofuran (THF);
Described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and the sodium hydrogen carbonate solution.
Preferably, among the described step S2:
Described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
Carbazole unit phenyl-difluoride and the triazolyl multipolymer of containing provided by the invention, because 1,2,3-benzotriazole polymkeric substance contains two fluorine atoms, its HOMO energy level will reduce 0.11eV, and fluorine replaces 1,2, the 3-benzotriazole has again two strong electrophilic imido grpups, 1,2 of fluorine replacement, the 3-benzotriazole is a heterogeneous ring compound that strong electrophilic performance is arranged, and the upper alkyl chain of introducing easily of the N of the N-H key of benzotriazole, this alkyl chain functional groups can improve the effciency of energy transfer of sun power, thereby solves the polymer solar battery low efficiency problem, simultaneously, the alkyl chain functional groups can also play regulates the solvability that contains carbazole unit phenyl-difluoride and triazolyl multipolymer, so that this polymkeric substance is conducive to film forming processing, enlarges them in the range of application in polymer solar field.
In addition, preparation method of the present invention adopts better simply synthetic route, thereby reduces technical process, and material is cheap and easy to get, reduces manufacturing cost.
Above-mentionedly containing the carbazole unit phenyl-difluoride and the triazolyl multipolymer can be used as the organic solar batteries active layer material, mainly is the electron donor material in the active coating.
In order to understand better the content of patent of the present invention, further specify technology case of the present invention below by concrete example and legend, specifically comprise material preparation and device preparation, but these embodiments do not limit the present invention, wherein, but the monomer reference literature (Adv.Mater. of compd A, 2007,19,2295) the synthetic purchase from the market of disclosed method obtains, but monomer reference literature (J.Am.Chem.Soc., 2011 of compd B, 133,4625) disclosed method is synthetic or buy from the market and obtain.
Embodiment 1
Present embodiment contain carbazole unit phenyl-difluoride and triazolyl multipolymer, i.e. poly-{ N-n-octyl-2,7-carbazole-co-2-n-octyl-4,7-dithienyl-5,6-difluoro benzotriazole }, wherein, R 1Be octane base, R 2Be the octane base, n is 63, and its structural formula is as follows:
Figure BDA0000093965260000071
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000093965260000072
With 2,7-hypoboric acid pinacol ester-9-n-octyl carbazole (159.3mg, 0.3mmol), 2-n-octyl-4,7-two (5-bromothiophene base)-5,6-two fluoro-1,2,3-benzotriazole (176 8mg, 0.3mmol), three dibenzalacetones, two palladium (13.75mg, 0.015mmol) and tri-butyl phosphine (being 2-dicyclohexyl phosphorus-2 ', 6 '-dimethoxy-biphenyl) (2mg) add and fill in the flask of 12mL toluene, and be dissolved into solution, and then with salt of wormwood (3mL, 2mol/L) solution joins in the solution, in the flask behind the logical about 30min of nitrogen purge gas, 100 ℃ of lower stirrings, Suzuki coupling reaction 48h, stop polyreaction after the cooling, obtain reaction solution.
In flask, add 40mL methyl alcohol, reaction solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after will collecting at last is poly-{ N-n-octyl-2 behind 50 ℃ of dry 24h under vacuum, 7-carbazole-co-2-n-octyl-4,7-dithienyl-5,6-difluoro benzotriazole } product, productive rate is 70%.
Test result is: molecular weight (GPC, THF, R.I): M n=42.2kDa, M w/ M n=2.1.
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of the multipolymer of embodiment 1 preparation; Conjugated polymers is located stronger absorption peak about 609nm as seen from Figure 2.
Embodiment 2
Present embodiment contain carbazole unit phenyl-difluoride and triazolyl multipolymer, i.e. poly-{ N-methyl-2,7-carbazole-co-2-NSC 62789 base-4,7-dithienyl-5,6-difluoro benzotriazole }, wherein, R 1Be methyl, R 2Be the NSC 62789 base, n is 70, and its structural formula is as follows:
Figure BDA0000093965260000081
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,7-hypoboric acid pinacol ester-9-methyl carbazole (86mg, 0.2mmol), 2-NSC 62789 base-4,7-two (5-bromothiophene base)-5,6-two fluoro-1,2,3-benzotriazole (151.4mg, 0.2mmol) add in the flask of the DMF solvent that fills 15ml, be dissolved into solution; And then yellow soda ash (2mL, 2mol/L) solution joined in the solution, the evacuated flask deoxygenation also is filled with argon gas, then add 5mg bi triphenyl phosphine dichloride palladium, at 110 ℃ of lower stirrings, Suzuki coupling reaction 24h, stop polyreaction after the cooling, obtain reaction solution.
In flask, add 50mL methyl alcohol, reaction solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after will collecting at last is poly-{ N-methyl-2 behind 50 ℃ of dry 24h under vacuum, 7-carbazole-co-2-NSC 62789 base-4,7-dithienyl-5,6-difluoro benzotriazole } product, productive rate 74%.
Test result is: molecular weight (GPC, THF, R.I): M n=51.8kDa, M w/ M n=2.0.
Embodiment 3
Present embodiment contain carbazole unit phenyl-difluoride and triazolyl multipolymer, i.e. poly-{ N-NSC 62789 base-2,7-carbazole-co-2-methyl-4,7-dithienyl-5,6-difluoro benzotriazole }, wherein, R 1Be NSC 62789 base, R 2Be methyl, n is 50, and its structural formula is as follows:
Figure BDA0000093965260000091
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000093965260000092
With 2,7-hypoboric acid pinacol ester-9-NSC 62789 base carbazole (209.7mg, 0.3mmol), 2-methyl-4,7-two (5-bromothiophene base)-5,6-two fluoro-1,2,3-benzotriazole (147.3mg, 0.3mmol) adds in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, and then sodium bicarbonate (3mL, 2mol/L) solution joined in the solution logical nitrogen and argon gas gas mixture, behind the about 20min of air-discharging, then the 17mg tetra-triphenylphosphine palladium is added in the two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, behind the about 10min of continuation air-discharging, 80 ℃ of lower stirrings, Suzuki coupling reaction 72h obtains reaction solution.
In flask, add 40mL methyl alcohol, reaction solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after will collecting at last is poly-{ N-NSC 62789 base-2 behind 50 ℃ of dry 24h under vacuum, 7-carbazole-co-2-methyl-4,7-dithienyl-5,6-difluoro benzotriazole } product, productive rate is 78%.
Test result is: molecular weight (GPC, THF, R.I): M n=38.8kDa, M w/ M n=2.0.
Embodiment 4
Present embodiment contain carbazole unit phenyl-difluoride and triazolyl multipolymer, i.e. poly-{ N-n-hexyl-2,7-carbazole-co-2-n-decane base-4,7-dithienyl-5,6-difluoro benzotriazole }, wherein, R 1Be n-hexyl, R 2Be the n-decane base, n is 10, and its structural formula is as follows:
Figure BDA0000093965260000101
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000093965260000111
With 2,7-hypoboric acid pinacol ester-9-n-hexyl carbazole (100.6mg, 0.2mmol), 2-n-decane base-4,7-two (5-bromothiophene base)-5,6-two fluoro-1,2,3-benzotriazole (123.4mg, 0.2mmol) add in the flask of the DMF solvent that fills 15ml, be dissolved into solution; And then with yellow soda ash (2mL, 2mol/L) solution joins in the solution, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (0.01mmol, 7.02mg), be heated to 130 ℃ of stirrings, Suzuki coupling reaction 12h, stop polyreaction after the cooling, obtain reaction solution.
In flask, add 50mL methyl alcohol, reaction solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after will collecting at last is poly-{ N-n-hexyl-2 behind 50 ℃ of dry 24h under vacuum, 7-carbazole-co-2-n-decane base-4,7-dithienyl-5,6-difluoro benzotriazole } product, productive rate 60%.
Test result is: molecular weight (GPC, THF, R.I): M n=8.5kDa, M w/ M n=2.4.
Embodiment 5
Present embodiment contain carbazole unit phenyl-difluoride and triazolyl multipolymer, i.e. poly-{ N-normal-butyl-2,7-carbazole-co-2-dodecyl-4,7-dithienyl-5,6-difluoro benzotriazole }, wherein, R 1Be normal-butyl, R 2Be dodecyl, n is 100, and its structural formula is as follows:
Figure BDA0000093965260000121
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
Figure BDA0000093965260000122
With 2,7-hypoboric acid pinacol ester-9-normal-butyl carbazole (142.5mg, 0.3mmol), 2-dodecyl-4,7-two (5-bromothiophene base)-5,6-two fluoro-1,2,3-benzotriazole (193mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, and then sodium bicarbonate (3mL, 2mol/L) solution is joined in the solution, logical nitrogen and argon gas gas mixture, behind the about 20min of air-discharging, then tetra-triphenylphosphine palladium (0.003mmol, 3.7mg) is added in the two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, after continuing the about 10min of air-discharging, 70 ℃ of lower stirrings, Suzuki coupling reaction 96h obtains reaction solution.
In flask, add 40mL methyl alcohol, reaction solution is carried out precipitating process, then filter by apparatus,Soxhlet's, afterwards successively with methyl alcohol and normal hexane extracting precipitation 24h; Then continue take chloroform colourless as solvent extraction is precipitated to, collect chloroformic solution and be spin-dried for and obtain red powder, red powder after will collecting at last is poly-{ N-normal-butyl-2 behind 50 ℃ of dry 24h under vacuum, 7-carbazole-co-2-dodecyl-4,7-dithienyl-5,6-difluoro benzotriazole } product, productive rate is 83%.
Test result is: molecular weight (GPC, THF, R.I): M n=67.9kDa, M w/ M n=1.9.
Embodiment 6
The organic solar batteries of present embodiment 6, its poly-{ N-n-octyl-2,7-carbazole-co-2-n-octyl-4,7-dithienyl-5,6-difluoro benzotriazole } (being DFBTz-Cz1) that adopts embodiment 1 to make is the electron donor material of active coating.
See also Fig. 3, this organic solar batteries comprises glass-base 11, transparent anode 12, middle supplementary layer 13, active coating 14 and the negative electrode 15 that stacks gradually.Transparent anode 12 can adopt tin indium oxide (referred to as ITO), is preferably the tin indium oxide that square resistance is 10-20 Ω/; Middle supplementary layer 13 adopts poly-3,4-Ethylenedioxy Thiophene and polystyrene-sulfonic acid matrix material (referred to as PEDOT:PSS); Active coating 14 comprises electron donor material and electron acceptor material, and electron donor material adopts the polymkeric substance (being DFBTz-Cz1) of embodiment 1 preparation, and electron acceptor material can be [6,6] phenyl-C 61-methyl-butyrate (referred to as PCBM); Negative electrode 15 can adopt aluminium electrode or double-metal layer electrode, such as Ca/Al or Ba/Al etc., and its thickness is preferably 170nm, 30nm, 130nm or 60nm.
Glass-base 11 can be used as bottom, during making, choose ito glass, and after ultrasonic cleaning, process supplementary layer 13 in the middle of ito glass applies with oxygen-Plasma, in the middle of again the polymkeric substance of embodiment 1 preparation and electron acceptor material being coated on after by blend on the supplementary layer 13, form active coating 14, and then by vacuum evaporation technology deposition cathode 15 on active coating 14, obtain above-mentioned solar cell device.This solar cell device also needs through heating under 110 degrees centigrade of air tight conditions 4 hours, drop to again room temperature, can effectively increase order and the regularity arranged between interior each group of molecule and molecule segment after device is annealed, improve transmission speed and the efficient of carrier mobility, and then improve photoelectric transformation efficiency.In the present embodiment, the thickness of negative electrode 15Al layer is respectively 170nm.
As shown in Figure 2, under illumination, light transmission glass-base 11 and ITO electrode 12, the conduction hole type electroluminescent material absorbing light energy in the active coating 14, and produce exciton, these excitons are moved to electron donor(ED)/acceptor material at the interface again, and with transfer transport to electron acceptor material, such as PCBM, realize the separation of electric charge, thereby form freely current carrier, i.e. freely electronics and hole.These freely electronics along electron acceptor material to metallic cathode transmission and collected by negative electrode, the hole is along electron donor material to ito anode transmission and collected by anode freely, thereby forms photoelectric current and photovoltage, realizes opto-electronic conversion, during external load 16, can power to it.In this process, conduction hole type electroluminescent material 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.
Table 1 is the photovoltaic attribute of the organic solar batteries of present embodiment 6.(annotate: PCE is effciency of energy transfer, V OcBe open circuit voltage, J ScBe short-circuit current, FF is packing factor.)
Table 1
Table 1 is the result show, at AM1.5,100mW/cm 2Under the illumination, be that the effciency of energy transfer of the organic solar batteries of electron donor material is 3.5% based on DFBTz-Cz1; Wherein, AM is that air quality refers to that sun light beam passes atmospheric optical path, arrives the ratio value representation of the optical path that sea level passed through with this optical path and the sun its light beam when the zenith; The AM1.5 condition refers to demarcate and test irradiance and the spectral distribution that the solar cell defined is used on ground; Its sun power solar global irradiance is 1000 watts every square metre, and the measurement temperature of solar cell is 25 degree; This standard is that International Electrotechnical Commission formulates, and what China adopted at present is this standard; A bit concrete, a standard sun is equivalent to the irradiation intensity of AM1.5G standard light source, and AM1.5G represents that zenith angle (angle of incident beam between incident light source and ground normal) is the sunlight of 48 degree, and light intensity is 1000W/m 2(be AM1.5,100mW/cm 2Illumination).
Should be understood that above-mentioned statement for preferred embodiment of the present invention is comparatively detailed, can not therefore think the restriction to scope of patent protection of the present invention, scope of patent protection of the present invention should be as the criterion with claims.

Claims (10)

  1. One kind have a following structural formula (I) contain carbazole unit phenyl-difluoride and triazolyl multipolymer:
    Figure FDA0000093965250000011
    In the formula, R 1, R 2Be C 1～C 20Alkyl, n is 10～100 integer.
  2. 2. carbazole unit phenyl-difluoride and the triazolyl multipolymer of containing according to claim 1 is characterized in that n is 50～70.
  3. 3. a preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer is characterized in that, comprises the steps:
    S1, the compd A and the compd B that provide following structural formula to represent respectively,
    Figure FDA0000093965250000012
    Wherein, in the described compd A, R 1Be C 1～C 20Alkyl; In the described compd B, R 2Be C 1～C 20Alkyl;
    S2, under oxygen-free environment, with described compd A and compd B according to 1: 1 add-on of mol ratio, be added in the organic solvent that contains catalyzer and alkaline solution, in carrying out the Suzuki coupling reaction under 70～130 ℃ after 12～96 hours, obtain having following structural formula described carbazole unit phenyl-difluoride and the triazolyl multipolymer of containing of (I):
    Figure FDA0000093965250000021
    In the formula, n is 10～100 integer.
  4. 4. the preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer according to claim 3 is characterized in that, also comprises the steps:
    S3, describedly contain the carbazole unit phenyl-difluoride and the triazolyl multipolymer carries out purification process to what obtain among the step S2.
  5. 5. according to claim 3 or the 4 described preparation methods that contain carbazole unit phenyl-difluoride and triazolyl multipolymer, it is characterized in that among the described step S2, described catalyzer is organic palladium, perhaps described catalyzer is the mixture of organic palladium and organophosphor ligand.
  6. 6. the preparation method who contains carbazole unit phenyl-difluoride and triazolyl multipolymer according to claim 5 is characterized in that, among the described step S2, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100.
  7. 7. according to claim 3 or the 4 described preparation methods that contain carbazole unit phenyl-difluoride and triazolyl multipolymer, it is characterized in that among the described step S2, described organic solvent is selected from least a in toluene, DMF and the tetrahydrofuran (THF).
  8. 8. according to claim 3 or the 4 described preparation methods that contain carbazole unit phenyl-difluoride and triazolyl multipolymer, it is characterized in that among the described step S2, described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and the sodium hydrogen carbonate solution.
  9. 9. according to claim 3 or the 4 described preparation methods that contain carbazole unit phenyl-difluoride and triazolyl multipolymer, it is characterized in that among the described step S2, described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
  10. 10. claimed in claim 1ly contain carbazole unit phenyl-difluoride and the application of triazolyl multipolymer in the organic solar batteries active coating.
CN201110286591XA 2011-09-23 2011-09-23 Difluoro-benzo-triazole-based copolymer containing carbazole unit, preparation method thereof and application thereof Pending CN103012749A (en)

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