SYNTHESIS OF POLYISOBUTYLENE WITH SEC-ARYLAMINO TERMINAL GROUP BY COMBINATION OF CATIONIC POLYMERIZATION WITH ALKYLATION

• Published in: 高分子科学（英文版） Vol. 27; no. 4; pp. 551 - 559
• Main Authors: Cheng-long Zhang, Yi-xian Wu, Xiao-yan Meng, Qiang Huang, Guan-ying Wu, Ri-wei Xu
• Format: Journal Article
• Language: English
• Published: Beiting University of Chemical Technology,State Key Laboratory of Chemical Resource Engineering,Beijing 100029,China 2009
• Subjects: Cationic polymerization; Polyisobutylene; Diphenylamine; Alkylation
• ISSN: 0256-7679; 1439-6203
• DOI: 10.3321/j.issn:0256-7679.2009.04.013

O6; The highly reactive polyisobutylenes (PIBs) with 6t-double bonds (87.5 mol%) or tert-chloro (tert-Cl) groups (95 mol%) could be prepared via the cationic polymerization of isobutylene (IB) coinitiated by BF3 or TiCl4 respectively. The Friedel-Crafts alkylation of diphenylamine (DPA) with the highly reactive PIB with α-double bonds was further conducted under different conditions, such as at different alkylation temperature, in the mixed solvents of CH2Cl2/n-hexane with different solvent polarity and at DPA concentration ([DPA]). The resultant PIBs with sec-arylamino terminal groups were characterized by GPC with RI/UV dual detectors and 1H-NMR spectrum. The experimental results indicated that alkylation efficiency increased with increases in reaction temperature, solvent polarity and [DPA]. The 77 mol% of sec-arylamino terminated PIBs could be obtained in 10/90 (V/V) mixture of nHex/CH2Cl2 with [DPA]/[PIB] of 3.0 at 60℃ for 45 h. Moreover, the alkylation of DPA with highly reactive PIBs with mainly tert-CI terminal groups was also carried out in 10/90 (V/V) mixture of CH2/Cl2/nHex with [DPA]/[PIB] = 3.0 at 60℃ for 45 h, and almost monoalkylation with 100 mol% sec-arylamino terminal groups could be achieved. These results will help further explorations of the molecular engineering via combination of cationic polymerization with alkylation.