Cationic polymerization with titanium(iv) compounds: Living polymerization and possibility of stereoregulation

Abstract

AbstractThis paper deals with the development of living cationic polymerizations and the possibility of stereoregulation therein based on the modulation of the Lewis acid activators by their ligands. For this, titanium(IV) chlorides [TiCl4‐n(OR)n] with various alkoxy or aryloxy groups were synthesized and employed for the cationic polymerizations of isobutyl vinyl ether (IBVE) in conjunction with HCl‐IBVE adduct. Living polymerizations were feasible with the titanium chlorides [TiCl2(OR)2] disubstituted with isopropoxy or phenoxy groups in CH2Cl2 at −15°C. The meso (isotactic) contents of the polymers obtained with TiCl2(OR)2 at −78°C became larger (up to 86%) with bulkier o‐substituents of phenoxy groups on the titanium compounds.