CN101928382A - Block conjugated polymer, and preparation method and use thereof - Google Patents
Block conjugated polymer, and preparation method and use thereof Download PDFInfo
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Abstract
The present invention provides a kind of block conjugated polymers and preparation method thereof for being used to prepare efficient organic photovoltaic devices, and structure is shown in formula I,
(Formulas I) wherein, the fragrant ring element of Ar representation polymer main chain is benzene, thiophene, fluorenes, carbazole, silicon aromatic heterocycle or thiazole heterocycle class aromatic structure; R1, R2 are the substituent group of [1,2,5] thiadiazoles [3,4-g] quinoxaline and diazosulfide respectively, respectively selected from one of hydrogen atom, saturated alkane, double bond alkane, three key alkane, ether oxygen chain, alkyl streptamine and sulfydryl class formation; M, n are the structural repeat unit number of main polymer chain, and m+n numerical value is greater than or equal to 4 integer and m ≥0, n ≥0. The polymer is preferably matched with solar spectrum, reduces the steric hindrance of polymer, improves the crystal property of polymer, has broad application prospects on photoelectric functional device, especially polymer solar battery.
Description
Technical field
The present invention relates to a kind of polymkeric substance of preparing organic photovoltaic devices and its production and use that is used to.
Background technology
Because to the needs of the renewable energy utilization of cheapness, increasing researcher has turned to sight in the field of efficient, cheap photovoltaic device.The advantage that has cheapness, easy preparation based on the organic photovoltaic system of polymkeric substance than inorganic semiconductor material, simultaneously, the potential advantages of organic photovoltaic devices are that it can prepare large-area flexible device, and this is that inorganic semiconductor material is beyond one's reach.In the last few years, the photoelectric transformation efficiency of organic photovoltaic devices was constantly soaring, had reached 6% at present.But in the report of just present organic solar batteries, the relatively poor solar spectrum coupling of polymer active layer is a shortcoming the most outstanding.Polymkeric substance all is the narrow polymkeric substance of a class absorption spectrum in the present report, and this base polymer has only absorbed the small portion energy of solar radiation.The polymkeric substance that has research group to prepare a series of arrowband system at this problem is widened the extinction scope of polymer active layer.The polymkeric substance of arrowband system can increase its absorption at the sunlight of long wave direction, but also there is a fatal weakness in its simultaneously, has lost at shortwave especially at the sunlight of 450-650nm scope.In addition, other some investigators prepare double-deck solar device by the structure that changes device and improve its absorption to sunlight, thereby improve its effective rate of utilization to sunlight.But, the preparation process more complicated of double-deck solar cell, the double-deck solar cell of formulations prepared from solutions is owing to the uncompatibility of solvent is not approved widely.Therefore, start with, find that a kind of not only can to have widened its absorption spectrum but also be unlikely to lose polymkeric substance be to prepare the effective way of organic photovoltaic devices efficiently in the method that the shortwave direction absorbs from the structure of polymkeric substance.
Summary of the invention
The purpose of this invention is to provide a kind of polymkeric substance of organic photovoltaic devices efficiently that is used to prepare,, do not lose the absorptive character of existing this base polymer simultaneously in the shortwave direction to widen the absorption spectrum of existing this base polymer.
The polymkeric substance that is used to prepare organic photovoltaic devices efficiently provided by the invention is the block conjugated polymer as shown in the formula the I structure,
Wherein, the aromatic nucleus unit of Ar representation polymer main chain is benzene, thiophene, fluorenes, carbazole, silicon aromatic heterocycle or thiazole heterocycle class aromatic structure; R
1, R
2Be respectively the also substituted radical of [3,4-g] quinoxaline and diazosulfide of [1,2,5]-thiadiazoles, be respectively and be selected from a kind of in hydrogen atom, saturated alkane, two key alkane, triple bond alkane, ether oxygen chain, alkyl streptamine and the sulfydryl class formation; M, n are the structural repeat unit number of main polymer chain, and m+n numerical value is integer and m 〉=0 more than or equal to 4, n 〉=0.
Preferably, described block conjugated polymer is the polymkeric substance of formula II structure,
Here, R is that carbonatoms is the saturated alkyl of 1-32, and m+n numerical value is integer and m 〉=0 more than or equal to 4, n 〉=0.
Or be the polymkeric substance of formula III structure,
Here, R is that carbonatoms is the saturated alkyl of 1-32, and m+n numerical value is integer and m 〉=0 more than or equal to 4, n 〉=0.
The preparation method of the block conjugated polymer of formula II structure, be with 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes, 4,7-two (5-bromo thiophene-2-yl)-5,6-two (alkoxyl group)-[1,2,5]-diazosulfide, 4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles also [3,4-g] quinoxaline is in reaction 24-48 hour under the 100-120C temperature under the tetrakis triphenylphosphine palladium catalysis, obtains the block conjugated polymer of formula II structure.
The preparation method of the block conjugated polymer of formula III structure is with 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes, 4,7-two (5-bromo thiophene-2-yl)-[1,2,5]-diazosulfide, 4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles also [3,4-g] quinoxaline obtain the block conjugated polymer of formula III structure in reaction 24-48 hour under the 100-120C temperature under the tetrakis triphenylphosphine palladium catalysis.
4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles also [3,4-g]-quinoxaline is prepared by following steps:
1) thionyl chloride is splashed in the pyridine solution that is dissolved with O-Phenylene Diamine, obtain benzo [c] [1,2,5] thiadiazoles after the reacting by heating;
2) benzo [c] [1,2,5] thiadiazoles is added in the Hydrogen bromide, reflux and stir, slow then dropping liquid bromine, reaction obtains 4,7-dibromo benzo [c] [1,2,5] thiadiazoles;
3) with 4,7-dibromo benzo [c] [1,2,5] thiadiazoles slowly adds in the mixing solutions of the vitriol oil, concentrated nitric acid, and room temperature reaction obtains 4,7-two bromo-5,6-dinitrobenzene benzo [c] [1,2,5] thiadiazoles;
4) 4,7-two bromo-5,6-dinitrobenzene benzo [c] [1,2,5] thiadiazoles, tributyl (thiophene-2-yl) tin add in the toluene, under the tetrakis triphenylphosphine palladium catalysis under the 100-120C temperature reaction obtained 5 in 24-48 hour, 6-dinitrobenzene-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles;
5) with 5,6-dinitrobenzene-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles add in the Glacial acetic acid, add iron powder reaction under the condition of 80 degree and obtain 5,6-diamino-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles;
6) with 5,6-diamino-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles joins in the Glacial acetic acid, adds diketone, and room temperature reaction obtains 6,7-dialkyl group-4,9-two (thiophene-2-yl)-[1,2,5] thiadiazoles is [3,4-g] quinoxaline also;
8) with 6,7-dialkyl group-4,9-two (thiophene-2-yl)-[1,2,5] thiadiazoles also [3,4-g] quinoxaline, bromo-succinimide join in the mixed solvent of trichloromethane and Glacial acetic acid, and room temperature reaction obtains 4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles [3,4-g]-quinoxaline also.
2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes can be according to document (Hou, Q.; Xu, Y.; Yang, W.; Yuan, M.; Peng, J.; Cao, Y.J.Mater.Chem., 2002,12,2887) synthesize.
Described block conjugated polymer can be used in preparation photoelectric functional device, for example be used to prepare polymer solar battery, specifically 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 IT0 conductive glass, prepare the film of one deck homogeneous by spin coating or other modes, steam the mode of crossing by vacuum then and on polymkeric substance, prepare metal electrode, can obtain the polymer organic solar cell.
The present invention carries out side group to the acceptor diazosulfide and modifies, the block conjugated polymer that obtains with modify before compare, widened absorption spectrum, do not lose simultaneously the absorptive character of shortwave direction, improved solvability, reduced the steric hindrance of alkyl chain, improve the crystal properties, improved photoelectric transformation efficiency.So polymkeric substance provided by the invention will have wide practical use in the photoelectric functional device.
Description of drawings
Fig. 1 is preparation 4,9-two (5-bromo thiophene-2-yl)-6, and 7-dioctyl-[1,2,5]-thiadiazoles is the reaction formula of [3,4-g] quinoxaline also;
Fig. 2 is the reaction formula of the block conjugated polymer of preparation formula II structure;
Fig. 3 is the reaction formula of the block conjugated polymer of preparation formula III structure;
The ultraviolet-visible absorption spectroscopy figure of the polymkeric substance that Fig. 4 makes for embodiment 2;
The ultraviolet-visible absorption spectroscopy figure of the polymkeric substance that Fig. 5 makes for embodiment 3;
The ultraviolet-visible absorption spectroscopy figure of the polymkeric substance that Fig. 6 makes for embodiment 4;
Fig. 7 is the voltage-to-current graphic representation of the device of the polymer manufacture that makes with embodiment 2.
Embodiment
Embodiment 1, preparation 4,9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1,2,5]-thiadiazoles is [3,4-g] quinoxaline also
4,9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1,2,5]-thiadiazoles also [3,4-g] quinoxaline are the important module of polymkeric substance in synthetic, and its preparation feedback formula as shown in Figure 1.
Specifically describe as follows:
Under the step 1) ice bath, thionyl chloride (240ml) is slowly splashed in the pyridine solution (240ml) that is dissolved with the 60g O-Phenylene Diamine,-after hour dripping off, back flow reaction 72 hours is poured reactant in the ice-water bath into, and a large amount of brown solids of separating out filter, column chromatography for separation obtains benzo [c] [1,2,5] thiadiazoles, yield is about 80%;
Step 2) benzo [c] [1,2,5] thiadiazoles 30g is added in 150ml (48%) Hydrogen bromide, reflux and stir, slow then dropping liquid bromine 42ml is added dropwise to complete back back flow reaction 2.5 hours, be cooled to room temperature, the aqueous solution that adds S-WAT filters, and obtains 4 with 500ml chloroform dissolving-recrystallization, 7-dibromo benzo [c] [1,2,5] thiadiazoles, yield is about 55%;
Under the step 3) condition of ice bath, with 4,7-dibromo benzo [c] [1,2,5] thiadiazoles 10g slowly add the vitriol oil, concentrated nitric acid (V: V=1: among the mixing solutions 100ml 1), room temperature reaction 8 hours, reaction product is poured on the ice cube, treat ice cube melt filter thick product, recrystallization obtains 4 in the ethanol, 7-two bromo-5,6-dinitrobenzene benzo [c] [1,2,5] thiadiazoles, yield about 29%;
Step 4) is 2.5g 4,7-two bromo-5,6-dinitrobenzene benzo [c] [1,2,5] thiadiazoles, 6.0g tributyl (thiophene-2-yl) tin add in the toluene, are reacting 24-48 hour under the 100-120C temperature under the tetrakis triphenylphosphine palladium catalysis, after being back to room temperature, use dichloromethane extraction, column chromatography for separation obtains 5,6-dinitrobenzene-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles, yield is about 95%;
Step 5) is 5,6-dinitrobenzene-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles 0.9g adds in the 40ml Glacial acetic acid, adds the 2.0g iron powder in batches and reacts 3.5 hours under the condition of 80 degree, be cooled to room temperature, extracted with diethyl ether is spin-dried for and obtains 5,6-diamino-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles, yield is about 95%;
Step 6) is 0.76g 5,6-diamino-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles joins in the 100ml Glacial acetic acid, adds 1.29g 9,10-dicarbapentaborane octadecane, room temperature reaction 5 hours, dichloromethane extraction three times, be spin-dried for column chromatography for separation and obtain 6,7-dioctyl-4,9-two (thiophene-2-yl)-[1,2,5] thiadiazoles also [3,4-g] quinoxaline, yield is about 95%;
Step 7) is 1.8g 6,7-dioctyl-4,9-two (thiophene-2-yl)-[1,2,5] thiadiazoles also [3,4-g] quinoxaline, 1.24g bromo-succinimide join trichloromethane and Glacial acetic acid mixed solvent 200ml (V: V=1: 1), lucifuge, room temperature reaction 24 hours, dichloromethane extraction three times is spin-dried for that column chromatography for separation obtains 4,9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1,2,5]-and thiadiazoles [3,4-g]-quinoxaline also, yield is about 85%.
Block conjugated polymer (the m: n=1) of embodiment 2, preparation formula II structure
The ternary conjugated polymers of formula II 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, 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two octane Oxy-1s, 3,5-diazosulfide and 4,9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1,2,5]-thiadiazoles also [3,4-g]-terpolymer of quinoxaline, its preparation feedback formula is as shown in Figure 2.Specifically describe as follows:
With 4 of 1mmol; 7-two (5-bromo thiophene-2-methylene radical)-5; 6-two octane Oxy-1s; 3; the 5-diazosulfide; 2 of 2mmol, 7-two (4,4; 5; 5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9; the 9-dioctyl fluorene; 4 of 1mmol; 9-two (5-bromo thiophene-2-yl)-6; 7-dioctyl-[1,2,5]-thiadiazoles also [3; 4-g]-sodium bicarbonate of quinoxaline and 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, and heating reflux reaction was cooled to room temperature after three days; with the sedimentation three times in acetone of trichloromethane dissolving back, obtain block conjugated polymer formula II.
Block conjugated polymer (the m: n=3) of embodiment 3, preparation formula II structure
The m of formula II structure: the ternary conjugated polymers of n=3 ratio 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, 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two octane Oxy-1s, 3,5-diazosulfide and 4,9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1,2,5]-thiadiazoles also [3,4-g]-terpolymer of quinoxaline, its preparation feedback formula is as shown in Figure 2.Specifically describe as follows:
With 4 of 0.5mmol; 7-two (5-bromo thiophene-2-methylene radical)-5; 6-two octane Oxy-1s; 3; the 5-diazosulfide; 2 of 2mmol, 7-two (4,4; 5; 5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9; the 9-dioctyl fluorene; 1.5mmol 4; 9-two (5-bromo thiophene-2-yl)-6; 7-dioctyl-[1,2,5]-thiadiazoles also [3; 4-g]-sodium bicarbonate of quinoxaline and 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, and heating reflux reaction was cooled to room temperature after three days; with the sedimentation three times in acetone of trichloromethane dissolving back, obtain block conjugated polymer formula II.
Block conjugated polymer (the m: n=0.33) of embodiment 4, preparation formula II structure
The m of formula II structure: the ternary conjugated polymers of n=0.33 ratio is to have 2, and 7-two (4,4,5,5-tetramethyl--l, 3,2-two oxa-s borine-2-yl)-9,9-dioctyl fluorene, 4,7-two (5-bromo thiophene-2-methylene radical)-5,6-two octane Oxy-1s, 3,5-diazosulfide and 4,9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1,2,5]-thiadiazoles also [3,4-g]-terpolymer of quinoxaline, its preparation feedback formula is as shown in Figure 2.Specifically describe as follows:
With 4 of 1.5mmol; 7-two (5-bromo thiophene-2-methylene radical)-5; 6-two octane Oxy-1s; 3; the 5-diazosulfide; 2 of 2mmol, 7-two (4,4; 5; 5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9; the 9-dioctyl fluorene; 0.5mmol 4; 9-two (5-bromo thiophene-2-yl)-6; 7-dioctyl-[1,2,5]-thiadiazoles also [3; 4-g]-sodium bicarbonate of quinoxaline and 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, and heating reflux reaction was cooled to room temperature after three days; with the sedimentation three times in acetone of trichloromethane dissolving back, obtain block conjugated polymer formula II.
Block conjugated polymer (the m: n=1) of embodiment 5, preparation formula III structure
The ternary conjugated polymers 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, 4,7-two (5-bromo thiophene-2-methylene radical)-1,3,5-diazosulfide and 4,9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1,2,5]-and the thiadiazoles terpolymer of [3,4-g]-quinoxaline also, its preparation feedback formula is as shown in Figure 3.Specifically describe as follows:
With 4 of 1mmol; 7-two (5-bromo thiophene-2-methylene radical)-1,3, the 5-diazosulfide; 2 of 2mmol; 7-two (4; 4,5,5-tetramethyl--1; 3; 2-two oxa-s borine-2-yl)-9, the 9-dioctyl fluorene; 4 of 1mmol; 9-two (5-bromo thiophene-2-yl)-6,7-dioctyl-[1; 2; 5]-thiadiazoles also the sodium bicarbonate of [3,4-g]-quinoxaline 10mmol join 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, in acetone sedimentation three times, obtain the block conjugated polymer formula III with trichloromethane dissolving back.
The ultraviolet-visible absorption spectroscopy of embodiment 2,3,4 described ternary block conjugated polymers is shown in Fig. 4,5,6, 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.The formula II block conjugated polymer that only prepares with embodiment 2 is that example illustrates the performance of conjugated polymers of the present invention as the active layer material of solar cell below.
3mg formula II block conjugated polymer (embodiment 2 preparations) and 12mg[6,6]-phenyl-C61-methyl-butyrate (being called for short PCBM) mixing, add the dissolving of 0.6ml orthodichlorobenzene, on the ITO of PEDOT:PSS modified conductive glass, preparing the thick film of the about 100nm of one deck by the spin coating mode, steam the mode of crossing by vacuum then and on polymkeric substance, prepare metal electrode, obtain solar cell with aluminium.
We adopt following condition the test of device (the above-mentioned polymer solar battery that makes):
(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, as shown in Figure 7, the performance of device shows as short-circuit current=11.3mA/cm
2Open circuit voltage=0.69V; Packing factor=0.41; Effciency of energy transfer=3.17%.Under the equal test condition, the device efficiency of nonheat-treated poly-(3-hexyl thiophene) is 1.59%.
Claims (8)
1. the block conjugated polymer of a formula I structure,
Wherein, the aromatic nucleus unit of Ar representation polymer main chain is benzene, thiophene, fluorenes, carbazole, silicon aromatic heterocycle or thiazole heterocycle class aromatic structure; R
1, R
2Be respectively the substituted radical of [1,2,5] thiadiazoles [3,4-g] quinoxaline and diazosulfide, be respectively and be selected from a kind of in hydrogen atom, saturated alkane, two key alkane, triple bond alkane, ether oxygen chain, alkyl streptamine and the sulfydryl class formation; M, n are the structural repeat unit number of main polymer chain, and m+n numerical value is integer and m 〉=0 more than or equal to 4, n 〉=0.
2. block conjugated polymer according to claim 1 is characterized in that: described block conjugated polymer is the polymkeric substance of formula II structure,
Here, R is that carbonatoms is the saturated alkyl of 1-32, and m+n numerical value is integer and m 〉=0 more than or equal to 4, n 〉=0.
3. block conjugated polymer according to claim 1 is characterized in that: described block conjugated polymer is the polymkeric substance of formula III structure,
Here, R is that carbonatoms is the saturated alkyl of 1-32, and m+n numerical value is integer and m 〉=0 more than or equal to 4, n 〉=0.
4. the preparation method of the described block conjugated polymer of claim 2, be with 2,7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes, 4,7-two (5-bromo thiophene-2-yl)-5,6-two (alkoxyl group)-[1,2,5]-diazosulfide, 4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles also [3,4-g] quinoxaline is in reaction 24-48 hour under 100120 ℃ of temperature under the tetrakis triphenylphosphine palladium catalysis, obtains the block conjugated polymer of formula II structure.
5. the preparation method of the described block conjugated polymer of claim 3 is with 2, and 7-two (4,4,5,5-tetramethyl--1,3,2-two oxa-s borine-2-yl)-9,9-dialkyl group fluorenes, 4,7-two (5-bromo thiophene-2-yl)-[1,2,5]-diazosulfide, 4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles also [3,4-g] quinoxaline obtain the block conjugated polymer of formula III structure in reaction 24-48 hour under 100-120 ℃ of temperature under the tetrakis triphenylphosphine palladium catalysis.
6. according to the described preparation method of claim 4, it is characterized in that: described 4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles also [3,4-g]-quinoxaline is prepared by following steps:
1) thionyl chloride is splashed in the pyridine solution that is dissolved with O-Phenylene Diamine, obtain benzo [c] [1,2,5] thiadiazoles after the reacting by heating;
2) benzo [c] [1,2,5] thiadiazoles is added in the Hydrogen bromide, reflux and stir, slow then dropping liquid bromine, reaction obtains 4,7-dibromo benzo [c] [1,2,5] thiadiazoles;
3) with 4,7-dibromo benzo [c] [1,2,5] thiadiazoles slowly adds in the mixing solutions of the vitriol oil, concentrated nitric acid, and room temperature reaction obtains 4,7-two bromo-5,6-dinitrobenzene benzo [c] [1,2,5] thiadiazoles;
4) 4,7-two bromo-5,6-dinitrobenzene benzo [c] [1,2,5] thiadiazoles, tributyl (thiophene-2-yl) tin add in the toluene, under the tetrakis triphenylphosphine palladium catalysis under 100-120 ℃ of temperature reaction obtained 5 in 24-48 hour, 6-dinitrobenzene-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles;
5) with 5,6-dinitrobenzene-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles add in the Glacial acetic acid, add iron powder reaction under the condition of 80 degree and obtain 5,6-diamino-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles;
6) with 5,6-diamino-4,7-two (thiophene-2-yl)-benzo [c] [1,2,5] thiadiazoles joins in the Glacial acetic acid, adds diketone, and room temperature reaction obtains 6,7-dialkyl group-4,9-two (thiophene-2-yl)-[1,2,5]-thiadiazoles is [3,4-g] quinoxaline also;
8) with 6,7-dialkyl group-4,9-two (thiophene-2-yl)-[1,2,5]-thiadiazoles also [3,4-g] quinoxaline, bromo-succinimide join in the mixed solvent of trichloromethane and Glacial acetic acid, and room temperature reaction obtains 4,9-two (5-bromo thiophene-2-yl)-6,7-dialkyl group-[1,2,5]-thiadiazoles [3,4-g]-quinoxaline also.
7. the application of the described block conjugated polymer of claim 1 in preparation photoelectric functional device.
8. application according to claim 7 is characterized in that: described photoelectric functional device is a polymer solar battery.
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| WO2012028246A1 (en) * | 2010-09-04 | 2012-03-08 | Merck Patent Gmbh | Conjugated polymers |
| CN102827356A (en) * | 2012-08-30 | 2012-12-19 | 西安近代化学研究所 | Conjugated polymer of 9-heptadecyl carbazole and chloroquinoxaline |
| CN103130986A (en) * | 2011-11-30 | 2013-06-05 | 海洋王照明科技股份有限公司 | 2,7-fluorine and dithienyl thiazole-thiazole copolymer and preparing method thereof and solar cell comprising the same |
| WO2013078635A1 (en) * | 2011-11-30 | 2013-06-06 | 海洋王照明科技股份有限公司 | Co-polymer of 2,7-carbazole and dithienyl thiazolothiazole, and method for preparing same and solar battery containing same |
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| US9837613B2 (en) | 2010-09-04 | 2017-12-05 | Merck Patent Gmbh | Conjugated polymers |
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| CN103288856B (en) * | 2012-02-28 | 2019-04-09 | 精工爱普生株式会社 | Thiadiazoles system compound, light-emitting component compound, light-emitting component, light emitting device, authentication device, electronic equipment |
| JP2014009163A (en) * | 2012-06-27 | 2014-01-20 | Sankyo Kasei Kk | Method for producing naphthobisthiadiazole |
| WO2014002969A1 (en) * | 2012-06-27 | 2014-01-03 | 三協化成株式会社 | Method for producing naphtho bis thiadiazole |
| CN102827356A (en) * | 2012-08-30 | 2012-12-19 | 西安近代化学研究所 | Conjugated polymer of 9-heptadecyl carbazole and chloroquinoxaline |
| CN105431467A (en) * | 2013-07-31 | 2016-03-23 | 株式会社Lg化学 | Copolymer and organic solar cell comprising same |
| CN107580622A (en) * | 2015-05-06 | 2018-01-12 | 默克专利股份有限公司 | Thiadiazoles and quinoxaline derivant |
| CN107580622B (en) * | 2015-05-06 | 2021-03-23 | 默克专利股份有限公司 | Thiadiazole quinoxaline derivative |
| CN110741028A (en) * | 2017-06-01 | 2020-01-31 | 住友化学株式会社 | Method for producing polymer compound |
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| CN114085360A (en) * | 2021-10-12 | 2022-02-25 | 中国科学院大学 | Narrow-bandgap conjugated polymer and organic photoelectric synapse device prepared from same |
| CN114085360B (en) * | 2021-10-12 | 2023-08-01 | 中国科学院大学 | Narrow band gap conjugated polymer and organic photoelectric synaptic device prepared from same |
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