Abstract
By using the cationic lutetium allyl species (C5Me4–C5H4N)Lu(η3-C3H5)2 (1)/[Ph3C][B(C6F5)4], the copolymerization of isoprene (IP) with styrene (St) could be achieved in a full range of monomer feed ratios (10 mol %–90 mol %). The 13C NMR and DSC analyses, and the competitive polymerization ratios (rSt = 3.1 vs rIP = 23.9) clearly revealed that the obtained IP–St copolymers were multiblocked microstructure with high cis-1,4-polyisoprene (PIP) units (80%) and crystalline syndiotactic polystyrene (sPS) sequences, which was in contrast to the copolymerization behavior of butadiene (BD) and St with the same system that afforded only diblock copolymer. Strikingly, the terpolymerization of St with IP and BD via coordination mechansim was realized for the first time with high conversions (74–85%) and high activities (111–144 kg (molLu h)−1). The 13C NMR spectroscopic analysis indicated that the resultant terpolymers were composed of perfect sPS blocks, high cis-1,4-PIP units (77.7%) and almost pure cis-1,4-polyb...
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