Abstract: | The end-functionalization of living polymers with bases (methanol, benzylamine, diethyl sodiomalonate, and sodium methoxide) and organosilicon compounds X ? Si(CH3)3;X ? : CH2?C(CH3)COO? , CH3COO? , CH2?CHCH2? , C6H5? ] was investigated in the living cationic polymerization of styrene initiated with the 1-phenylethyl chloride/SnCl4/nBu4NCl system in CH2Cl2 at ?15°C. The four bases and C6H5SiMe3, independent of their structures, were apparently incapable of reacting with the living end and invariably led to polystyrenes with the ω-end chlorine ~ ~ ~ CH2CH(Ph)Cl] originated from the initiating system. The number-average end-functionality (F?n) of the chloride, determined by 1H-NMR, was close to unity (F?n > 0.9). The presence of chlorine in the polymer was also confirmed by elemental analysis. In contrast, the quenching by the trimethylsilyl compounds with X = methacryloxy, acetoxy, and allyl gave ω-end-functionalized polystyrenes with the corresponding terminal groups (X) for which the F?n values were close to unity (F?n > 0.9). The effects of the structure of silyl compounds on end-capping are also discussed. © 1994 John Wiley & Sons, Inc. |