CN101875716A - Block conjugated polymer, preparation method thereof and use thereof - Google Patents
Block conjugated polymer, preparation method thereof and use thereof Download PDFInfo
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- CN101875716A CN101875716A CN2009100832789A CN200910083278A CN101875716A CN 101875716 A CN101875716 A CN 101875716A CN 2009100832789 A CN2009100832789 A CN 2009100832789A CN 200910083278 A CN200910083278 A CN 200910083278A CN 101875716 A CN101875716 A CN 101875716A
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Abstract
The invention discloses a block conjugated polymer, a preparation method thereof and use thereof. The structural general formula of the block conjugated polymer is represented by a formula I. In the invention, diazosulfide serving as a receptor is subjected to side-group modification, the obtained block conjugated polymer is improved in dissolubility and crystallinity and reduced in steric hindrance of the alkyl chains, and thus high organic solar cell efficiency is achieved. Therefore, the block conjugated polymer provided by the invention has a promising application prospect in solar cells.
Description
Technical field
The present invention relates to class block conjugated polymer and preparation method thereof and application.
Background technology
Sun power has caused numerous investigators' interest as a kind of renewable energy source, and solar cell also arises at the historic moment thereupon.Organic polymer solar cell than the inorganic silicon solar cell, have plasticity-and advantage such as cheap, but effciency of energy transfer is also lower, does not reach the requirement of application.So, design new polymer architecture, improve battery efficiency, become the hot issue of current organic polymer solar cell research field.The document of the comprehensive polymer organic solar cell of having reported, the structure of its design mainly contains following several: (i) be main chain with the Polythiophene, 3 side groups of thiophene are changed (Hou, J.; Tan, Z.; Yan, Y.; He, Y.; Yang, C.; Li, Y.J.Am.Chem.Soc., 2006,128,4911); Be backbone structure (ii), carry out texture improvement (Shen, P. with PPV (poly-phenylene vinylene (ppv)); Sang, G.; Lu, J.; Zhao, B.; Wan, M.; Zou, Y.; Li, Y.; Tan, S.Macromolecules, 2008,41,5716) (iii) be the conjugated polymers of elementary cell with the donor-receiver, acceptor is generally diazosulfide (Peet, the J. of electron-withdrawing group; Kim, J.Y.; Coates, N.E.; Ma, W.L.; Moses, D.; Heeger, A.J.; Bazan, G.C.Nat.Mater., 2007,6,497).Wherein, the polymkeric substance of the third type is widely studied, and has obtained higher efficient.But, polymkeric substance with the third type, often in order to change solvability, can on to body unit, introduce the alkyl chain side group, thereby reduced the crystal property of main polymer chain, for example be polymkeric substance with carbazole in the document, on carbazole unit, introduced two alkyl chains to body, efficient only is 3.6% (Blouin, N.; Michaud, A.; Leclerc, M.Adv.Mater., 2007,19,2295.).
Summary of the invention
The purpose of this invention is to provide a kind of block conjugated polymer and preparation method thereof and application.
Block conjugated multipolymer provided by the invention, its general structure be suc as formula shown in the I,
In the formula I general structure, Ar is phenyl, thienyl, fluorenyl, carbazyl, silicon fragrant heterocyclic radical or thiazole heterocycle aromatic base;
R is the alkyl of C1-C32, the alkylene of C2-C32, alkynes base, ether oxygen base, alkyl streptamine or the sulfydryl of C2-C32; N is more than or equal to 4 and smaller or equal to 100 integer.
This block conjugated polymer can be shown in formula II or the formula III general structure;
(formula II)
In formula II and the formula III general structure, R ' is the saturated alkane base of 1-32 for carbonatoms, and n is more than or equal to 4 and smaller or equal to 100 integer.
The method of block conjugated polymer shown in the preparation formula II provided by the invention is under the katalysis of tetrakis triphenylphosphine palladium, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-and 9-alkyl-9H-carbazole and described 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the 5-diazosulfide reacts, and obtains described block conjugated polymer.
In this method, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-9-alkyl-9H-carbazole and 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the mol ratio of 5-diazosulfide is 1: 0.99-1.05, preferred 1: 1; The consumption of described tetrakis triphenylphosphine palladium is 2, the 0.8-1.2% of the mole dosage of 7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-9-alkyl-9H-carbazole.Temperature of reaction is 100-120 ℃, and the reaction times is 24-48 hour.This reaction is carried out in organic solvent; Described organic solvent is that any one or two kinds in tetrahydrofuran (THF) or the toluene mix with arbitrary proportion and the mixtures of water.
The method for preparing block conjugated polymer shown in the formula III provided by the invention is under the katalysis of tetrakis triphenylphosphine palladium, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes and described 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the 5-diazosulfide reacts, and obtains described block conjugated polymer.
In this method, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes and 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the mol ratio of 5-diazosulfide is 1: 0.99-1.05, preferred 1: 1; The consumption of tetrakis triphenylphosphine palladium is 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9, the 0.8-1.2% of the mole dosage of 9-dialkyl group fluorenes.Temperature of reaction is 100-120 ℃, and the reaction times is 24-48 hour.This reaction is carried out in organic solvent; Described organic solvent is that any one or two kinds in tetrahydrofuran (THF) or the toluene mix with arbitrary proportion and the mixtures of water.
In above-mentioned reactions steps, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-9-alkyl-9H-carbazole synthesizes according to the method that following document provides: Synthesis ofDiindolocarbazoles by Cadogan Reaction:Route to Ladder Oligo (p-aniline) s, Bouchard, J.; Wakim, S.; Leclerc, M.J.Org.Chem., 2004,69,5705.
2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes synthesizes according to the method that following document provides: Novel red-emitting fluorene-based copolymers, Hou, Q.; Xu, Y.; Yang, W.; Yuan, M.; Peng, J.; Cao, Y.J.Mater.Chem., 2002,12,2887.
Among the above-mentioned preparation method, reactant 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the structural formula of 5-diazosulfide be suc as formula shown in the IV,
(formula IV)
This compound is prepared as follows:
1) with nitric acid and 1, the 2-dimethoxy benzene reacts, and obtains 1,2-dimethoxy-4 ', 5-dinitrobenzene;
2) with 1, the 2-dimethoxy-4 ', 5-dinitrobenzene, glass putty and hydrochloric acid react in organic solvent, obtain 4,5-dimethoxy benzene-1, the hydrochloride of 2-diamines;
3) with 4,5-dimethoxy benzene-1, the hydrochloride and the thionyl chloride of 2-diamines react in organic solvent, obtain 5,6-dimethoxy-1,2,5-diazosulfide;
4) with 5,6-dimethoxy-1,2,5-diazosulfide and Hydrogen bromide react, and obtain 5,6-dihydroxyl-1,2,5-diazosulfide;
5) with 5,6-dihydroxyl-1,2,5-diazosulfide, bromo alkane, potassiumiodide and salt of wormwood react in organic solvent, obtain 5,6-dialkoxy-1,2,5-diazosulfide;
6) with 5,6-dialkoxy-1,2,5-diazosulfide and liquid bromine react in organic solvent, obtain 4,7-two bromo-5,6-dialkoxy-1,2,5-diazosulfide;
7) under the katalysis of tetrakis triphenylphosphine palladium, with 5,6-dialkoxy-1,2,5-diazosulfide, thiophene-2-base-2-boric acid react, and obtain 5,6-dialkoxy-4,7-two (thiophene-2-yl)-1,2,5-diazosulfide;
8) with 5,6-dialkoxy-4,7-two (thiophene-2-yl)-1,2,5-diazosulfide and bromo-succinimide react in organic solvent, obtain 4 ,-two (5-bromo thiophenes-2-methylene radical)-5,6-dialkoxy-1,3,5-diazosulfide.
In the step 1) of this method, described nitric acid and 1, the ratio of 2-dimethoxy benzene is 400ml-1000ml:5g-10g, preferred 900ml:10g; Temperature of reaction is 60-100 ℃, preferred 80; Reaction times is 1 hour-10 hours, preferred 2 hours;
Step 2) in, described 1, the 2-dimethoxy-4 ', the ratio of 5-dinitrobenzene, glass putty and hydrochloric acid is 0.1mol-1mol:2mol-5mol:300ml-900ml, preferred 0.4mol:3.2mol:560ml; Described 1, the 2-dimethoxy-4 ', the volumetric molar concentration of 5-dinitrobenzene in described organic solvent is 1-2mol/L, preferred 1mol/L; Described temperature of reaction is 60-100 ℃, preferred 80 ℃; Reaction times is 0.5 hour-2 hours, preferred 1 hour;
In the step 3), described 4,5-dimethoxy benzene-1, the hydrochloride of 2-diamines and the ratio of thionyl chloride are 20g-60g:300ml-800ml, preferred 40g:500ml; Described 4,5-dimethoxy benzene-1, the volumetric molar concentration of the organic solution of the hydrochloride of 2-diamines is 0.05-0.2g/L, preferred 0.08g/L; Described temperature of reaction is a room temperature; Reaction times is 48 hours-96 hours, preferred 72 hours; Described organic solvent is a pyridine;
In the step 4), described 5,6-dimethoxy-1,2,5-diazosulfide and hydrobromic ratio are 10g-40g:200ml-800ml, preferred 20g:400ml; Described temperature of reaction is 70-110 ℃, preferred 90 ℃; Reaction times is 24 hours-72 hours, preferred 48 hours;
In the step 5), described 5,6-dihydroxyl-1,2, the mol ratio of 5-diazosulfide, bromo alkane, potassiumiodide and salt of wormwood is 10-30: 10-30: 0.1-0.3: 20-60; Described 5,6-dihydroxyl-1,2, the volumetric molar concentration of 5-diazosulfide in organic solvent is 0.1-0.3mol/L; Described temperature of reaction is 100-200 ℃, preferred 140 ℃; Reaction times is 24 hours-72 hours, preferred 48 hours; Described organic solvent is N, dinethylformamide;
In the step 6), described 5,6-dialkoxy-1,2, the mol ratio of 5-diazosulfide and liquid bromine is 1: 2.2-3, preferred 1: 2.5; Described 5,6-dialkoxy-1,2, the volumetric molar concentration of 5-diazosulfide in described organic solvent is 0.05-0.2mol/L, preferred 0.1mol/L; Described temperature of reaction is a room temperature; Reaction times is 24 hours-72 hours, preferred 48 hours; Described organic solvent is that methylene dichloride and acetate are with arbitrary proportion blended mixed solvent;
In the step 7), described 5,6-dialkoxy-1,2, the mol ratio of 5-diazosulfide, thiophene-2-base-2-boric acid, tetrakis triphenylphosphine palladium is 1-2: 2.0-5: 10-20, preferred 1: 2.5: 10; Described temperature of reaction is 80-100 ℃, and the reaction times is 24-48 hour, preferred 48 hours;
In the step 8), described 5,6-dialkoxy-4,7-two (thiophene-2-yl)-1,2, the mol ratio of 5-diazosulfide and bromo-succinimide is 1: 2-3, preferred 1: 2.2; Described 5,6-dialkoxy-4,7-two (thiophene-2-yl)-1,2, the volumetric molar concentration of the organic solution of 5-diazosulfide is 0.05-0.2mol/L, preferred 0.1mol/L; Described temperature of reaction is a room temperature; Reaction times is 2 hours-20 hours, preferred 10 hours; Described organic solvent is a trichloromethane.
In addition, application, especially the application in polymer solar battery of block conjugated polymer provided by the invention in preparation photoelectric functional device also belongs to protection scope of the present invention.
With polymer application of the present invention when the organic solar batteries, can carry out as follows: polymkeric substance and C60 and derivative thereof or other the material that can be used as electron acceptor(EA) are mixed, add dissolution with solvents, on the ITO conductive glass, prepare the film of one deck homogeneous by spin coating or other modes, mode by vacuum evaporation prepares metal electrode on polymkeric substance then, can obtain the polymer organic solar cell.
The present invention carries out side group to the acceptor diazosulfide and modifies, alkyl chain is incorporated on the position of diazosulfide, the block conjugated polymer that obtains, not only improved solvability, simultaneously because the reduction of alkyl chain sterically hindered, improve the crystal properties, thereby obtained very high organic solar batteries efficient.Thereby block conjugated polymer polymkeric substance provided by the invention will have wide practical use in solar cell.
Description of drawings
Fig. 1 is the ultraviolet-visible absorption spectroscopy figure of embodiment 1 polymkeric substance;
Fig. 2 is the ultraviolet-visible absorption spectroscopy figure of embodiment 2 polymkeric substance;
Fig. 3 is the voltage-to-current curves of embodiment 3 devices under two kinds of test conditions.
Embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.
Block conjugated polymer shown in embodiment 1, the preparation formula II
The block conjugated polymer of formula II structure is to have 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-9-octyl group-9H-carbazole and 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (hot alkoxyl group)-1,2, the copolymer of 5-diazosulfide, its preparation feedback formula is as follows:
Specifically describe as follows:
Under the step 1) ice bath, with nitric acid (65%, 900ml) be added drop-wise to 1, among the 2-dimethoxy benzene 10g, after dripping off in one hour, be heated to 80 ℃ of reactions two hours, be cooled to room temperature, reactant is poured in the ice-water bath, a large amount of yellow solids of separating out filter, and obtain 1 with ethyl alcohol recrystallization then, the 2-dimethoxy-4 ', the 5-dinitrobenzene, yield about 80%.
Step 2) with 1; the 2-dimethoxy-4 ', 5-dinitrobenzene 0.4mol and glass putty 3.2mol join in the ethanol, and nitrogen protection adds concentrated hydrochloric acid 560ml down; heating reflux reaction 1h under the nitrogen protection; after reducing to room temperature, revolve and steam alcohol solvent, add the hydrochloric acid 400ml of 3mol/l; obtain 4 with behind the ethyl acetate extraction three times; 5-dimethoxy benzene-1, the hydrochloride of 2-diamines, yield are about 85%.
Under the step 3) ice bath, with 4 of 40g, 5-dimethoxy benzene-1, the hydrochloride of 2-diamines join in the pyridine solution of 500ml, and the thionyl chloride of 500ml slowly splashes in the pyridine solution, and after dripping off in 2 hours, reaction is three days under the room temperature.Reaction soln is poured in the frozen water, filtered the solid ethyl alcohol recrystallization that obtains, obtain 5,6-dimethoxy-1,2,5-diazosulfide, yield are about 75%.
Step 4) is with 5 of 20g, 6-dimethoxy-1,2, the 5-diazosulfide joins in the Hydrogen bromide (48%) of 400ml, is heated to 90 ℃ of reactions two days, separate out a large amount of brown white solids in the reaction, the solid 5 that filtration obtains, 6-dihydroxyl-1,2, the 5-diazosulfide is directly used in step 5, and yield is about 78%.
Step 5) is with 5 of 20mmol; 6-dihydroxyl-1; 2; the bromine octane of the salt of wormwood of 5-diazosulfide, 40mmol, 0.2mmol potassiumiodide and 20mmol joins the N of 100ml; in the dinethylformamide; the following 140 ℃ of reactions of nitrogen protection two days; be cooled to room temperature, filter out salt of wormwood, behind ethyl acetate extraction; be spin-dried for solvent; use the ethyl acetate of 10: 1 volume ratios again: the mixed solvent 100ml crystallization of sherwood oil obtains solid 5,6-two octane Oxy-1s, 2; 5-diazosulfide, yield are about 85%.
Step 6) is with 5 of 20mmol, and 6-dialkoxy-1,2,5-diazosulfide are dissolved in the acetate mixed solvent of 200ml methylene dichloride and 10ml, adds 50mmol liquid bromine, room temperature lucifuge reaction two days.In the saturated aqueous solution of adding sodium bisulfite and behind the remaining liquid bromine, use dichloromethane extraction, after the solvent evaporated, obtain 4 with alcohol crystal, 7-two bromo-5,6-two octane Oxy-1s, 2,5-diazosulfide, yield are about 98%.
Step 7) is with 4 of 10mmol; 7-two bromo-5; 6-two octane Oxy-1s; 2; the sodium bicarbonate of the thiophene of 5-diazosulfide, 25mmol-2-base-2-boric acid and 100mmol joins in the mixed solvent of 50ml tetrahydrofuran (THF) and 10ml water; nitrogen protection adds the 0.1mmol tetrakis triphenylphosphine palladium down; heating reflux reaction two days, be back to room temperature after, use dichloromethane extraction; column chromatography for separation obtains 5; 6-two hot alkoxyl groups-4,7-two (thiophene-2-yl)-1,2; 5-diazosulfide, yield are about 60%.
Step 8) is 5 of 10mmol, 6-two hot alkoxyl groups-4,7-two (thiophene-2-yl)-1,2, the 5-diazosulfide is dissolved in the methylene dichloride of 100ml, adds the bromo-succinimide of 22mmol, room temperature reaction 10h under the lucifuge, the saturated aqueous solution of adding S-WAT, extraction, column chromatography for separation obtains 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two octane Oxy-1s, 3,5-diazosulfide, yield are about 90%.
Step 9) is with 4 of 1mmol; 7-two (5-bromo thiophene-2-methylene radical)-5; 6-two octane Oxy-1s; 3; the 5-diazosulfide; 2 of 1mmol; 7-two (4,4,5; 5-tetramethyl--1; 3,2-two oxa-s boryl-2-methylene radical)-9-octyl group-9H-carbazole; the sodium bicarbonate of 10mmol joins the tetrahydrofuran (THF) of 50ml; in the mixed solvent of the toluene of 10ml and the water of 10ml, nitrogen protection adds the catalyzer tetrakis triphenylphosphine palladium of 0.1mmol down; behind the heating reflux reaction three days; be cooled to room temperature, the acetone sedimentation is three times behind the trichloromethane, obtains block conjugated polymer shown in the formula II.
Block conjugated polymer shown in embodiment 2, the preparation formula III
The block conjugated polymer of formula III structure is to have 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dioctyl fluorene and 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two octane Oxy-1s, 3, the copolymer of 5-diazosulfide, its preparation feedback formula is as follows:
With 4 of 1mmol; 7-two (5-bromo thiophene-2-methylene radical)-5; 6-two octane Oxy-1s; 3; 2 of 5-diazosulfide, 1mmol, 7-two (4,4; 5; 5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9; the sodium bicarbonate of 9-dioctyl fluorene, 10mmol joins in the mixed solvent of water of the toluene of tetrahydrofuran (THF), 10ml of 50ml and 10ml; nitrogen protection adds the catalyzer tetrakis triphenylphosphine palladium of 0.1mmol down, and heating reflux reaction was cooled to room temperature after three days; the acetone sedimentation is three times behind the trichloromethane, obtains block conjugated polymer shown in the formula III.
Embodiment 3, preparation are the organic solar batteries of active layer material with conjugated polymers of the present invention
The ultraviolet-visible absorption spectroscopy of embodiment 1 and 2 described two kinds of block conjugated polymers respectively as illustrated in fig. 1 and 2, from the absorption spectrum as can be known, polymkeric substance has wide absorption peak in the visible region, this is very helpful to polymer solar battery is provided to the absorption of sunlight, can be used for the making of polymer solar battery.
Formula II block conjugated polymer and 7.5mg[6 that 3mg embodiment 1 is prepared, 6]-phenyl-C
61-methyl-butyrate (being called for short PCBM) mixes, add the dissolving of 0.6ml orthodichlorobenzene, on the ITO of PEDOT:PSS modified conductive glass, preparing the thick film of one deck 100nm by the spin coating mode, mode by vacuum evaporation prepares metal electrode with aluminium on polymkeric substance then, obtains solar cell.
Adopt following two kinds of conditions to carry out device detection:
Test condition 1: (freely open up the xenon source of scientific ﹠ technical corporation's purchase and the filter plate of 370nm-700nm from Beijing, proofread and correct with the standard silicon solar cell that science and technology group 18 of China Electronics is bought, light intensity is 100mW/cm to simulated solar irradiation
2) under, the performance of device shows as short-circuit current=17.3mA/cm
2Open circuit voltage=0.75V; Packing factor=0.54; Effciency of energy transfer=7.0%.Under the equal test condition, the device efficiency of poly-(3-hexyl thiophene) is 5.7%.
Test condition 2: (freely open up the xenon source that scientific ﹠ technical corporation buys from Beijing, do not add filter plate, proofread and correct with the irradiatometer that the Beijing Normal University optical instrument factory buys, light intensity is 100mW/cm to simulated solar irradiation
2) under, the performance of device shows as short-circuit current=12.1mA/cm
2Open circuit voltage=0.81V; Packing factor=0.61; Effciency of energy transfer=6.0%.Under the equal test condition, the device efficiency of poly-(3-hexyl thiophene) is 3.2%.
Claims (13)
1. the block conjugated multipolymer shown in the formula I general structure,
(formula I)
In the described formula I general structure, Ar is phenyl, thienyl, fluorenyl, carbazyl, silicon fragrant heterocyclic radical or thiazole heterocycle aromatic base;
R is the alkyl of C1-C32, the alkylene of C2-C32, alkynes base, ether oxygen base, alkyl streptamine or the sulfydryl of C2-C32; N is more than or equal to 4 and smaller or equal to 100 integer.
2. block conjugated polymer according to claim 1 is characterized in that: described block conjugated polymer is suc as formula shown in the II general structure;
In the described formula II general structure, R ' is the alkyl of 1-32 for carbonatoms, and n is more than or equal to 4 and smaller or equal to 100 integer.
3. block conjugated polymer according to claim 1 is characterized in that: described block conjugated polymer is shown in the formula III general structure;
In the described formula III general structure, R ' is the alkyl of 1-32 for carbonatoms, and n is more than or equal to 4 and smaller or equal to 100 integer.
4. a method for preparing the described block conjugated polymer of claim 2 is under the katalysis of tetrakis triphenylphosphine palladium, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-9-alkyl-9H-carbazole and claim 1 are described 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the 5-diazosulfide reacts, and obtains the described block conjugated polymer of claim 10.
5. method according to claim 4 is characterized in that: described 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-9-alkyl-9H-carbazole and claim 1 described 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the mol ratio of 5-diazosulfide is 1: 0.99-1.05, preferred 1: 1;
The consumption of described tetrakis triphenylphosphine palladium is 2, the 0.8-1.2% of the mole dosage of 7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s boryl-2-methylene radical)-9-alkyl-9H-carbazole.
6. according to claim 4 or 5 described methods, it is characterized in that: described temperature of reaction is 100-120 ℃, and the reaction times is 24-48 hour.
7. according to the arbitrary described method of claim 4-6, it is characterized in that: described reaction is carried out in organic solvent; Described organic solvent is that any one or two kinds in tetrahydrofuran (THF) or the toluene mix with arbitrary proportion and the mixtures of water.
8. a method for preparing the described block conjugated polymer of claim 3 is under the katalysis of tetrakis triphenylphosphine palladium, 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes and claim 1 described 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the 5-diazosulfide reacts, and obtains the described block conjugated polymer of claim 11.
9. method according to claim 8 is characterized in that: described 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes and claim 1 are described 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two (alkoxyl group)-1,2, the mol ratio of 5-diazosulfide is 1: 0.99-1.05, preferred 1: 1;
The consumption of described tetrakis triphenylphosphine palladium is 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9, the 0.8-1.2% of the mole dosage of 9-dialkyl group fluorenes.
10. according to Claim 8 or 9 described methods, it is characterized in that: described temperature of reaction is 100-120 ℃, and the reaction times is 24-48 hour.
11. arbitrary according to Claim 8-10 described method, it is characterized in that: described reaction is carried out in organic solvent; Described organic solvent is that any one or two kinds in tetrahydrofuran (THF) or the toluene mix with arbitrary proportion and the mixtures of water.
12. the application of the arbitrary described block conjugated polymer of claim 1-3 in preparation photoelectric functional device
13. application according to claim 12 is characterized in that: described photoelectric functional device is a polymer solar battery.
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| CN102153732A (en) * | 2011-01-10 | 2011-08-17 | 常州大学 | Copolymer of stereo-regular thiophene oligomer and benzothiadiazole and preparation method thereof |
| WO2012028246A1 (en) * | 2010-09-04 | 2012-03-08 | Merck Patent Gmbh | Conjugated polymers |
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