CN103159928A - Thiophene pyrroledione based co-polymer material, and preparation method and application thereof - Google Patents
Thiophene pyrroledione based co-polymer material, and preparation method and application thereof Download PDFInfo
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- 0 CC1(C)OB(c(cc2)cc3c2c2ccc(B4OC(C)(*)C(C)(C)O4)cc2[n]3*)OC1(C)C Chemical compound CC1(C)OB(c(cc2)cc3c2c2ccc(B4OC(C)(*)C(C)(C)O4)cc2[n]3*)OC1(C)C 0.000 description 7
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Abstract
The invention belongs to the field of solar cells, and discloses a thiophene pyrroledione based co-polymer material, and a preparation method and an application thereof. The co-polymer has the following structural formula (I). In the formula, both R1 and R2 represent a C1-C20 alkyl group and n is an integer ranging from 10 to 100. In the thiophene pyrroledione based co-polymer material provided by the invention, 2,7-carbazole has good hole transport properties, excellent chemical stability and easily modified photophysical properties; thiophene pyrroledione has a simple, symmetrical and polar structure and is beneficial to electron delocalization when the thiophene pyrroledione is polymerized with other monomers; and the thiophene pyrroledionehas relatively strong electron-withdrawing effect that results in reduction of an HOMO energy level and a LUMO energy level, thereby facilitating the increase of an open-circuit voltage. The performance can improve energy conversion efficiency of solar energy, so that the problem of low efficiency of polymer solar cells is solved.
Description
Technical field
The present invention relates to the solar cell material field, relate in particular to a kind of Thienopyrroles diketo multipolymer and its preparation method and application.
Background technology
Utilize cheap material preparation low cost, dynamical solar cell is study hotspot and the difficult point in photovoltaic field always.The silicon wafer battery that is used for ground at present is restricted its application because complex manufacturing, cost are high.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
The Thienopyrroles diketo multipolymer that provides a kind of effciency of energy transfer high is provided purpose one of the present invention.
A kind of Thienopyrroles diketo multipolymer with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
Another object of the present invention is to provide the preparation method of above-mentioned Thienopyrroles diketo multipolymer, comprise the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
Wherein, in described compd A, R
1Be C
1～C
20Alkyl; In 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, fully dissolving is rear after carrying out Suzuki coupling reaction 12～96h under 70～130 ℃, stop polyreaction after cooling, obtain the having following structural formula described Thienopyrroles diketo multipolymer of (I):
In formula, n is the integer of 10-100.
In the preparation method of above-mentioned Thienopyrroles diketo multipolymer, in described step S2:
Described catalyzer is organic palladium, and described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Described catalyzer also can be organic palladium (as, three dibenzalacetone two palladiums) and the organophosphor ligand mixture of (as, tri-butyl phosphine); In described mixture, described organic palladium is three dibenzalacetone two palladiums, described organophosphor ligand is tri-butyl phosphine, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8;
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF);
Described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
The preparation method of above-mentioned Thienopyrroles diketo multipolymer, preferably, in described step S2:
The preparation method of Thienopyrroles diketo 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 the application of above-mentioned Thienopyrroles diketo multipolymer in the organic solar batteries active coating.
Thienopyrroles diketo multipolymer provided by the invention is because 2,7-carbazole has good hole transport performance, superior chemical stability and the photophysical property of easily modifying.By adjusting the different body units that is subjected to, energy gap is easy to be regulated and controled.In addition, because the HOMO energy level of carbazyl is lower, thereby open circuit voltage (Voc) is higher.The Thienopyrroles diketone has simply, symmetrical, polar structure, is conducive to electron delocalization after its and other monomer polymerization, and it also has stronger sucting electronic effect and causes HOMO and lumo energy reduction, is conducive to like this raising of open circuit voltage.This performance can improve the effciency of energy transfer of sun power, thereby solves the polymer solar battery low efficiency problem.
In addition, in the preparation method of above-mentioned isoindigo base co-polymer, adopted better simply synthetic route, thereby reduced technical process, material is cheap and easy to get, reduces manufacturing cost, and the material structure that makes is novel, and solubility property is good, and film forming properties is good.
Description of drawings
Fig. 1 is preparation technology's schema that the present invention contains Thienopyrroles diketo multipolymer;
Fig. 2 is the energy transformation effect graphic representation of the multipolymer of embodiment 1 preparation
Fig. 3 is the organic solar energy cell structure schematic diagram of embodiment 7.
Embodiment
Principle of design of the present invention: thiophene [3,4-c] and pyrroles-4, the 6-diketone causes vast organic solar batteries investigators' concern in recent years because of its higher effciency of energy transfer: the advantages such as simple, compact, symmetry and plane configuration, after it and other monomer copolymerization, this advantage will be conducive to electron delocalization; In addition, it also has stronger sucting electronic effect, is conducive to reduce HOMO and lumo energy; Simultaneously, the N-H bond energy enough easily modifies to improve solvability and photoelectric properties with functional groups such as other alkyl.
The Thienopyrroles diketo multipolymer with following structural formula (I) that present embodiment provides:
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer; N is preferably 50～70.
The preparation method of above-mentioned Thienopyrroles diketo 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,
Wherein, in compd A, R
1Be C
1～C
20Alkyl; In 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, fully dissolving is rear after carrying out Suzuki coupling reaction 12～96h under 70～130 ℃, stop polyreaction after cooling, obtain mixed solution, comprise product in this mixed solution, namely have the described Thienopyrroles diketo multipolymer of following structural formula (I):
In formula, n is 10～100 integer;
S3, the product in step S2 is carried out purification process:
Add methyl alcohol in the mixed solution of step S2, 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, red powder after 50 ℃ of dry 24h under vacuum, is obtained the Thienopyrroles diketo multipolymer of purifying.
In the preparation method of above-mentioned Thienopyrroles diketo multipolymer, in described step S2:
Described catalyzer is organic palladium, and described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100; Described catalyzer also can be organic palladium (as, three dibenzalacetone two palladiums) and the organophosphor ligand mixture of (as, tri-butyl phosphine); In described mixture, described organic palladium is three dibenzalacetone two palladiums, described organophosphor ligand is tri-butyl phosphine, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8;
Described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF);
Described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
Preferably, in described step S2:
Described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
Above-mentioned Thienopyrroles diketo multipolymer can be used as the organic solar batteries active layer material, is mainly the electron donor material in active coating.
In order to understand better the content of patent of the present invention, further illustrate 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., 1997 of compd B, 119,5065.) disclosed method is synthetic or buy from the market and obtain.
Embodiment 1
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ N-n-octyl-2,7-carbazole-co-N-n-octyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be octane base, R
2Be the octane base, n is 55), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2, 7-hypoboric acid pinacol ester-9-n-octyl carbazole (159.3mg, 0.3mmol), N-n-octyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (126mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol), tri-butyl phosphine (18mg, 0.09mmol) add in the flask that fills 12mL toluene, fully after the dissolving with solution of potassium carbonate (3mL, 2mol/L) join in flask, then logical nitrogen purge gas is approximately after 30min, stir under 95 ℃, Suzuki coupling reaction 48h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed 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 collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ N-n-octyl-2,7-carbazole-co-N-n-octyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 84%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=30.2kDa, M
w/ M
n=2.0.
Fig. 2 is the energy transformation effect curve figure of the multipolymer of embodiment 1 preparation; Result shows, at AM1.5; 100mW/cm
2Under illumination, the effciency of energy transfer that is the body heterojunction solar cell of donor material based on the polymkeric substance of embodiment 1 is 3.5%; Zou etc. have reported that with 2,7-carbazyl multipolymer be donor material, and PCBM is that acceptor material has prepared solar cell, and effciency of energy transfer is 1.6%.(Macromolecules2009，42，2891-2894)
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ N-octyl group-2,7-carbazole-co-N-octyl group-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be methyl, R
2Be the NSC 62789 base, n is 40), its structural formula is as follows:
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) and N-NSC 62789 base-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (118mg, 0.2mmol) add in the flask of the DMF solvent that fills 15ml, be dissolved into solution; And then with sodium carbonate solution (2mL, 2mol/L) join in flask, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (5.6mg, 0.008mmol), stirring, Suzuki coupling reaction 24h, stop polyreaction after cooling under 120 ℃, obtains mixed solution.
Add 50mL methyl alcohol in flask, mixed 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 collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ N-octyl group-2,7-carbazole-co-N-octyl group-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate 75%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=26.1kDa, M
w/ M
n=2.2.
Embodiment 3
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ N-NSC 62789 base-2,7-carbazole-co-N-methyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be NSC 62789 base, R
2Be methyl, n is 80), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2, 7-hypoboric acid pinacol ester-9-NSC 62789 base carbazole (209.7mg, 0.3mmol) and N-methyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (98mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, and then with sodium hydrogen carbonate solution (3mL, 2mol/L) join in solution, logical nitrogen and argon gas gas mixture, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium tetra-triphenylphosphine palladium (4mg, 0.003mmol) add in two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, continue air-discharging approximately after 10min, stir under 70 ℃, Suzuki coupling reaction 96h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed 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 collecting at last is poly-{ N-eicosyl-2 after 50 ℃ of dry 24h under vacuum, 7-carbazole-co-N-methyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 73%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=49.0kDa, M
w/ M
n=2.1.
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ N-normal butane base-2,7-carbazole-co-N-dodecyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be normal butane base, R
2Be dodecyl, n is 100), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
With 2,7-hypoboric acid pinacol ester-9-normal-butyl carbazole (95mg, 0.2mmol) and N-dodecyl-2,5-two bromo-thiophene [3,4-c] and pyrroles-4,6-diketone (95.8mg, 0.2mmol) add in the flask of the DMF solvent that fills 15ml, be dissolved into solution; And then with sodium carbonate solution (2mL, 2mol/L) join in flask, the evacuated flask deoxygenation also is filled with argon gas, then add bi triphenyl phosphine dichloride palladium (7.2mg, 0.01mmol), stirring, Suzuki coupling reaction 12h, stop polyreaction after cooling under 130 ℃, obtains mixed solution.
Add 50mL methyl alcohol in flask, mixed 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 collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ N-normal butane base-2,7-carbazole-co-N-dodecyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate 70%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=54.8kDa, M
w/ M
n=2.1.
Embodiment 5
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ N-n-tetradecane base-2,7-carbazole-co-N-n-decane base-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be n-tetradecane base, R
2Be the n-decane base, n is 10), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2, 7-hypoboric acid pinacol ester-9-n-tetradecane base carbazole (180mg, 0.3mmol) and N-decyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (135mg, 0.3mmol) add in the two-mouth bottle of the 50mL specification that fills the 15mL tetrahydrofuran (THF), be dissolved into solution, and then with sodium hydrogen carbonate solution (3mL, 2mol/L) join in solution, logical nitrogen and argon gas gas mixture, air-discharging is approximately after 20min, then with tetra-triphenylphosphine palladium tetra-triphenylphosphine palladium (8mg, 0.006mmol) add in two-mouth bottle, fully lead to again nitrogen and argon gas gas mixture, continue air-discharging approximately after 10min, stir under 80 ℃, Suzuki coupling reaction 72h, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed 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 collecting at last is poly-{ N-n-tetradecane base-2 after 50 ℃ of dry 24h under vacuum, 7-carbazole-co-N-n-decane base-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 79%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=9.5kDa, M
w/ M
n=2.1.
The Thienopyrroles diketo multipolymer of the present embodiment, i.e. poly-{ N-normal hexane base-2,7-carbazole-co-N-n-hexadecyl-thiophene [3,4-c] and pyrroles-4,6-diketone } (wherein, R
1Be normal hexane base, R
2Be n-hexadecyl, n is 30), its structural formula is as follows:
The preparation process of above-mentioned polymkeric substance is as follows:
Reaction formula is as follows:
with 2, 7-hypoboric acid pinacol ester-9-normal hexane base carbazole (146.4mg, 0.3mmol), N-n-hexadecyl-2, 5-two bromo-thiophene [3, 4-c] and pyrroles-4, 6-diketone (160.6mg, 0.3mmol), three dibenzalacetone two palladium (13.75mg, 0.015mmol), tri-butyl phosphine (18mg, 0.09mmol) add in the flask that fills 12mL toluene, fully after the dissolving with solution of potassium carbonate (3mL, 2mol/L) join in flask, then logical nitrogen purge gas is approximately after 30min, stir under 110 ℃, Suzuki coupling reaction 24h, stop polyreaction after cooling, obtain mixed solution.
Add 40mL methyl alcohol in flask, mixed 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 collecting at last is under vacuum after 50 ℃ of dry 24h, be poly-{ N-normal hexane base-2,7-carbazole-co-N-n-hexadecyl-thiophene [3,4-c] and pyrroles-4, the 6-diketone } product, productive rate is 81%.
Test result is: Molecular weight (GPC, THF, R.I): M
n=20.6kDa, M
w/ M
n=2.1.
Embodiment 7
The organic solar batteries of the present embodiment 7, its poly-{ N-octyl group-2,7-carbazole-co-N-octyl group-thiophene [3,4-c] and pyrroles-4,6-diketone } that adopts that embodiment 1 makes 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 poly-{ N-octyl group-2,7-carbazole-co-N-octyl group-thiophene [3,4-c] and pyrroles-4, the 6-diketone } 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 applying with oxygen-Plasma on ito glass, in the middle of again the polymkeric substance of embodiment 1 preparation and electron acceptor material being coated on after by blend on 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 4h under 110 degrees centigrade of air tight conditions, 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 3, under illumination, light transmission glass-base 11 and ITO electrode 12, the conduction hole type electroluminescent material in active coating 14 absorbs luminous energy, and produces exciton, these excitons move to electron donor(ED)/acceptor material at the interface again, and with transfer transport to electron acceptor material, 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, 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.
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, and scope of patent protection of the present invention should be as the criterion with claims.
Claims (10)
1. Thienopyrroles diketo multipolymer with following structural formula (I):
In formula, R
1, R
2Be C
1～C
20Alkyl, n is 10～100 integer.
2. the preparation method of a Thienopyrroles diketo multipolymer, is characterized in that, comprises the steps:
S1, the compd A and the compd B that provide following structural formula to represent respectively,
Wherein, in described compd A, R
1Be C
1～C
20Alkyl; In described compd B, R
2Be C
1～C
20Alkyl;
S2, under oxygen-free environment, with described compd A and compd B according to the mol ratio add-on of 1: 1, add in the organic solvent that contains catalyzer and alkaline solution, fully dissolving is rear after carrying out Suzuki coupling reaction 12～96h under 70～130 ℃, stop polyreaction after cooling, obtain the having following structural formula described Thienopyrroles diketo multipolymer of (I):
In formula, n is 10～100 integer.
3. the preparation method of Thienopyrroles diketo multipolymer according to claim 2, is characterized in that, in described step S2, described catalyzer is organic palladium.
4. the preparation method of Thienopyrroles diketo multipolymer according to claim 3, it is characterized in that, in described step S2, described organic palladium is selected from bi triphenyl phosphine dichloride palladium or tetra-triphenylphosphine palladium, and the mol ratio of described organic palladium and described compd A is 1: 20～1: 100.
5. the preparation method of Thienopyrroles diketo multipolymer according to claim 2, is characterized in that, in described step S2, described catalyzer is the mixture of organic palladium and organophosphor ligand.
6. the preparation method of Thienopyrroles diketo multipolymer according to claim 5, it is characterized in that, in described mixture, described organic palladium is three dibenzalacetone two palladiums, described organophosphor ligand is tri-butyl phosphine, the mol ratio of described organic palladium and described compd A is 1: 20～1: 100, and the mol ratio of described organic palladium and organophosphor ligand is 1: 4～8.
According to claim 3 to 6 arbitrary described Thienopyrroles diketo multipolymer the preparation method, it is characterized in that, in described step S2, described organic solvent is selected from least a in toluene, DMF and tetrahydrofuran (THF).
According to claim 3 to 6 arbitrary described Thienopyrroles diketo multipolymer the preparation method, it is characterized in that, in described step S2, described alkaline solution is selected from least a in sodium carbonate solution, solution of potassium carbonate and sodium hydrogen carbonate solution.
According to claim 3 to 6 arbitrary described Thienopyrroles diketo multipolymer the preparation method, it is characterized in that, in described step S2, described Suzuki coupling reaction temperature is 80～110 ℃; The described Suzuki coupling reaction time is 24～72h.
10. the application of Thienopyrroles diketo multipolymer claimed in claim 1 in the organic solar batteries active coating.
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| CN114773580A (en) * | 2022-04-29 | 2022-07-22 | 太原理工大学 | Irregular ternary conjugated polymer photocatalytic material and preparation method and application thereof |
| CN114773580B (en) * | 2022-04-29 | 2024-04-30 | 太原理工大学 | Irregular ternary conjugated polymer photocatalytic material and preparation method and application thereof |
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