Cyclopentadiene dithiophene-thiarolobis(benzothiadiazole) copolymer and its preparation method and application
A technology of cyclopentadiene dithiophene and benzothiadiazole, which is applied in the field of cyclopentadiene dithiophene-thiarolodipolymer and its preparation, can solve the problems of low energy conversion efficiency, spectral response load, and mobility low level problem
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[0055] see figure 1 , the preparation method of the cyclopentadiene dithiophene-thiarolo two (benzothiadiazole) copolymer of one embodiment, comprises the steps:
[0056] Step S110: preparing compound A and compound B.
[0057] The structural formula of compound A is:
[0058]
[0059] Among them, R 1 and R 2 for C 1 ~C 20 the alkyl group; R 1 and R 2 Can be the same or different; R 1 and R 2 It is straight chain alkyl or branched chain alkyl.
[0060] Compound A was prepared using Compound C and Compound D as reactants. Wherein, the structural formula of compound C is:
[0061]
[0062] The structural formula of compound D is:
[0063]
[0064] Among them, R 1 and R 2 for C 1 ~C 20 the alkyl group; R 1 and R 2 Can be the same or different; R 1 and R 2 It is straight chain alkyl or branched chain alkyl.
[0065] In an inert gas (nitrogen, helium, argon, etc.) protective atmosphere, compound C was dissolved in the first solvent to obtain the first ...
Embodiment 1
[0109] Preparation of poly{4,4-dioctyl-cyclopentadieno[2,1-b;3,4-b']dithiophene-6,6dioctylthirolo[3,2-e:4 ,5-e] two (benzothiadiazole)}, the structural formula is:
[0110]
[0111] 1. Preparation of compound C—4,4’-dibromo-6,6’-diiodo-bi-2,1,3-benzothiadiazole
[0112] (1) Preparation of 5-nitro-2,1,3 benzothiadiazole
[0113] Add 2-amino-5-nitroaniline (22.95g, 0.15mol) and 100ml thionyl chloride (SOCl 2 ), stirred and slowly added 2ml of pyridine dropwise, heated and refluxed at 80-90°C for 24h, stopped the reaction, heated to 80°C and rotary evaporated excess SOCl 2 Afterwards, the reaction product was cooled to room temperature, poured into a large amount of water, stirred, filtered, washed with water and then vacuum-dried to obtain 21.7 g of the product 5-nitro-2,1,3-benzothiadiazole with a yield of 80%.
[0114] The reaction formula is as follows:
[0115]
[0116] (2) Preparation of 4,7-dibromo-5-nitro-2,1,3 benzothiadiazole
[0117] Add 5-nitro-2,1,3 benzot...
Embodiment 2
[0142] Preparation of poly{{4,4-bis(n-eicosyl)-cyclopentadieno[2,1-b; 3,4-b']dithiophene-6,6 dimethylthiarolo[3 ,2-e:4,5-e] two (benzothiadiazole)}, the structural formula is:
[0143]
[0144] 1. Preparation of compound C—4,4’-dibromo-6,6’-diiodo-bi-2,1,3-benzothiadiazole
[0145] The preparation method is the same as in Example 1.
[0146] 2. Preparation of compound A—4,8-dibromo-6,6-dimethylthiarolo[3,2-e:4,5-e]bis(benzothiadiazole)
[0147] Add 4,4'-dibromo-6,6'-diiodo-bi2,1,3 benzothiadiazole (compound C) (3.4g, 5mmol) and 50ml THF into a three-necked flask, and stir for 20min with nitrogen gas , slowly add n-butyllithium (4mL, 2.5M, 0.01mol) dropwise for half an hour, control the temperature at -90°C, keep stirring at -90°C for 2 hours, add 4.73ml of dimethyl dichloride Silane (compound D) (10 mmol), raised to room temperature, stirred for 10 hours. Stop the reaction, wash with water, extract with anhydrous ether, obtain an organic layer, dry over anhydrous sodium...
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