4,8-Diisooctyloxyphenyl[1,2-b:4,5-b']bithiophene and fluoroquinoxaline conjugated polymer
A technology of isooctyloxyphenyl and fluoroquinoxaline is applied in the application field of preparing polymer photovoltaic cells and achieves the effects of excellent performance and symmetrical structure
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Embodiment 1
[0038] Example 1: Polymer A
[0039] Step 1. Preparation of 6-fluoro-5,8-dibromo-2,3-bis(3-octyloxyphenyl)quinoxaline
[0040] The synthetic route is as follows:
[0041]
[0042] (1) Preparation of 4-fluoro-3,6-dibromo-1,2-phenylenediamine
[0043] 5-Fluoro-4,7-dibromo-2,1,3-benzothiadiazole (5g, 0.016mol) was dissolved in 150ml absolute ethanol, NaBH was added in batches at 0℃ 4 (11.1g, 0.29mol), then react at room temperature for 20h; after the reaction, concentrate to remove ethanol, add 160ml of water, extract with ethyl acetate, wash the organic phase with saturated brine, and finally use anhydrous MgSO 4 Drying; concentration to remove the organic solvent, the crude product obtained is purified by silica gel column chromatography, the eluent is n-hexane / ethyl acetate (the volume ratio of n-hexane to ethyl acetate is 25:1) to obtain 4-fluoro- 3.5 g of 3,6-dibromo-1,2-phenylenediamine, with a yield of 78%.
[0044] (2) Preparation of 1,2-bis(3-octyloxyphenyl)ethanedione
[0045] Li...
Embodiment 2
[0061] Example 2: Polymer B
[0062] The synthetic route is as follows:
[0063]
[0064] In this example, 6,7-difluoro-5,8-dibromo-2,3-bis(3-octyloxyphenyl)quinoxaline was used as the electricity-deficient unit, and the polymerization in step 3 of Example 1 was used. The method prepared polymer B with a yield of 85%, a number average molecular weight of 58563, and a molecular weight distribution of 1.96. Among them, the preparation method of 6,7-difluoro-5,8-dibromo-2,3-bis(3-octyloxyphenyl)quinoxaline adopts the method in step 1 of Example 1, the difference is that it uses 4,5-difluoro-3,6-dibromo-1,2-phenylenediamine instead of 4-fluoro-3,6-dibromo-1,2-phenylenediamine, 6,7-difluoro The NMR characterization data of -5,8-dibromo-2,3-bis(3-octyloxyphenyl)quinoxaline are: 1 HNMR(CDCl 3 ,500MHz,ppm),δ=7.32(m,4H),7.24(t,2H),6.98(m,2H),3.95(t,4H)1.76(m,4H),1.45(dd,4H),1.34 (m, 16H), 0.93 (t, 6H).
[0065] Electrochemical test: use CHI660D electrochemical workstation, use glassy carb...
Embodiment 3
[0067] Example 3: Polymer C
[0068] The synthetic route is as follows:
[0069]
[0070] In this example, 6-fluoro-5,8-dibromo-2,3-bis(4-octyloxyphenyl)quinoxaline was used as the electricity-deficient unit, and polymer C was prepared by the method in step 3 of Example 1 , The yield is 85%, the number average molecular weight is 45315, and the molecular weight distribution is 2.11.
[0071] Electrochemical test: use CHI660D electrochemical workstation, use glassy carbon electrode as working electrode, platinum wire electrode as counter electrode, Ag / Ag + The electrode is a reference electrode, Bu 4 N·PF 6 As an electrolyte, the HOMO energy of polymer C film measured by cyclic voltammetry in acetonitrile solvent is -5.20 eV, which is lower than -5.16 eV of non-fluorinated material B', which is 0.04 eV, see Table 1.
[0072] Photovoltaic performance research: using ITO / PEDOT:PSS / polymer:PC 61 BM / LiF / Al sandwich battery structure, combining polymer C and acceptor material PC 61 BM is ma...
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