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Styrene underwent unprecedented coordination-insertion copolymerization with naked polar monomers ( ortho-/ meta-/ para-methoxystyrene) in the presence of a pyridyl methylene fluorenyl yttrium catalyst. High activity (1.26×106 g molY−1 h−1) and excellent syndioselectivity were observed, and high-molecular-weight copolymers (24.6×104 g mol−1) were obtained. The insertion rate of the polar monomers could be adjusted in the full range of 0-100 % simply by changing the loading of the polar styrene monomer. Strikingly, the copolymers had tapered, gradient, and even random sequence distributions, depending on the position of the polar methoxy group on the phenyl ring and thus on its mode of coordination to the active metal center, as shown by tracking the polymerization process and DFT calculations. [ABSTRACT FROM AUTHOR]

Stereoselective coordination/insertion polymerization of the polar ortho-methoxystyrene has been achieved for the first time by using the cationic β-diketiminato rare-earth-metal species. High activity and excellent isoselectivity ( mmmm>99 %) were acheived. The unmasked Lewis-basic methoxy group does not poison the Lewis-acidic metal center, but instead activates the polymerization through σ-π chelation to the active species together with the vinyl group, thus lower the coordination and activation energies as compared with those of styrene derivatives lacking the methoxy group. [ABSTRACT FROM AUTHOR]