Stereoselective Copolymerization of Unprotected Polar and Nonpolar Styrenes by an Yttrium Precursor: Control of Polar‐Group Distribution and Mechanism

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. Take control: Methoxystyrenes underwent coordination–insertion copolymerization with styrene in the presence of a cationic yttrium catalyst to give copolymers with tapered, gradient, and even random sequence distributions, depending on the position of the methoxy substituent (see picture). The incorporation of the polar styrene could be adjusted between 0 and 100 % simply by changing the loading of this monomer.