Abstract: | The controlled cationic polymerization of isobutylene (IB) initiated by H2O as initiator and TiCl4 as coinitiator was carried out in n‐Hexane/CH2Cl2 (60/40, v/v) mixture at ?40 °C in the presence of N,N‐dimethylacetamide (DMA). Polyisobutylene (PIB) with nearly theoretical molecular weight (Mn = 1.0 × 104 g/mol), polydispersity (Mw/Mn) of 1.5 and high content (87.3%) of reactive end groups (tert‐Chlorine and α‐double bond) was obtained. The Friedel‐Crafts alkylation of triphenylamine (TPA) with the above reactive PIB was further conducted at different reactions, such as TPA]/PIB], solvent polarity, alkylation temperature, and time. The resultant PIBs with arylamino terminal group were characterized by 1H NMR, UV, and GPC with RI/UV dual detectors. The experimental results indicate that alkylation efficiency (Aeff) increased with increases in TPA]/PIB], reaction temperature, and reaction time and with a decrease in solvent polarity. The alkylation efficiency could reach 81.0% at 60/40(v/v) mixture of n‐Hex/CH2Cl2 with TPA]/PIB] of 4.49 at 50 °C for 54 h. Interestingly, the synthesis of PIB with arylamino terminal group could also be achieved in one pot by combination of the cationic polymerization of IB initiated by H2O/TiCl4/DMA system with the successive alkylation by further introduction of TPA. Mono‐, di‐ or tri‐alkylation occurred experimentally with different molar ratio of TPA]/PIB]. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 936–946, 2008 |