新型超支化电致发光聚合物的合成及性能研究.pdf

339 Wittig-Horner PPV 85% PLED 1 HP2 ABn PPV PPV [1-5] , , ,, [6-8] [9-12] A2+B3 HP2 2 2.1 1 4- ≥98 ≥98 N N- 3? 72 340 2.2 1H NMR Bruker NICOLET-210 - Waters 515-2410 THF Pyris Zahner 2.3 1 AV 600MHz PSt TGA Zahner IM6e KW-4A FT-IR Horiba U-3010 Horiba F-4500 GPC DSC Perkin Elmer PCT-IA OCH3 + HCl + OCH3 OH HO OH + OTs + HO TsO OTs B CH2Cl (EtO)2OP OCH3 2(EtO)3 P 1,4- H3CO A2II CH2Cl H3CO A2I OCH3 OHC OH HO NaH, DMF PO(OEt)2 3TsCl H3CO A2 OCH3 OTs TsO B OH K2CO3 DMF O OTs H3CO OCH3 O O O OCH3 OCH3 H3CO A2 OCH3 H3CO H3CO OH O X O y HP2 Fig. 1 Synthetic route of the monomers and polymer 2.3.1 A2 4.4-[p-1- -2- 2,5- ]- (A2) 1 1,4- -2,5- (A2II) 13.8g(0.1 mol) 125 mL 13 mL 50~60 6.9g(0.23 mol) 3 h 60 mL 78% 167.5-168.5 1H NMR(CDCl3, δ in ppm) 6.93(s,2H,ArH), 4.64(s,4H,ClCH2), 3.66 (s,6H,CH3) FT-IR(kBr,cm-1):3030,1136,880,2970,1514,1464,1261,1221, 1042 A2II 2 1,4-(2,5-2,5150 341 (C10H12O2Cl2)(235): Calcd. C 51.09, H 5.14; Found. C 50.99, H 5.18 ) (A2I) 18.53g 0.079 mol 1,4- 26.18g 0.158mol 7 100ml N2 65% 1H NMR(CDCl3, δ in ppm): 1.21-1.23(t, 12H, CH3),3.19-3.22(d, 4H, Ar-CH2P), 3.78(s, 6H, OCH3),3.98-4.03(m, 8H, CH2), 6.89(d, 2H, Ar-H) FT-IR(kBr, cm-1):3436 2982 1517 1268 1037 971 882 633 A2I 3 4.4-[p-1- (C18H32O8P2)(418): Calcd. C 49.32, H 7.30; Found. C 49.52, H 7.49 -2- 2,5- ]- (A2) 500ml 5.67g(0.236 mol) 15ml 70ml N,N- DMF 16.81g 38.46mmol 1,4-(2,5- ) 70ml N,N- 20 N2 2 10.38g 85.12mmol 40 16 70mlDMF 1N PH 6 -10 N,N- 57% 1H NMR(DMSO, δ in ppm): 3.87(s, 6H, -OCH3), 6.73(d, 4H, Ar-H), 7.15-7.22(dd, 2H, trans CH=C), 7.35(d, 4H, Ar-H), 7.15(s, 2H, central Ar-H), 9.56(s, 2H, OH-) FT-IR(kBr, cm-1):3368 3040 1659 1514 1407 1259 850 686 A2 2.3.2 (C22H18O2)(374): Calcd. C 77.00, H 5.88; Found. C 71.33, H 5.74 B3 1 1 1- B 4.02g 0.03mol 1 1 1- 10ml 17.16g 0.09mol 20ml 0 15ml 92% 1H NMR(DMSO, δ in ppm): 0.50(t, 3H, CH3), 1.20(q, 2H, CH3CH2), 2.43(s, 9H, CH3-ф), 3.76(s, 6H, OCH2-), 7.4-7.7(dd, 6H, Ar-H) FT-IR(kBr, cm-1): 3432, 2964, 1596, 1358, 1178, 976, 835, 556 B 2.3.3 (C27H32O9S