Polar comonomers regulate and control the copolymerization of conjugated dienes and methoxystyrenes catalyzed by a CGC-type rare-earth metal catalyst

(Co)polymerization of polar olefins has been catalyzed by rare-earth metal catalysts attributed to the high coordination number of the metal center and the heteroatom-facilitated effect. Herein, the regulation and controllability of polar comonomers in the copolymerization of conjugated dienes (CDs) (IP, MY, OC) and methoxystyrenes (o/m/pMOS, 2,5-F/Cl/Br/IMOS) were originally developed, in which the regioselectivity of CD units was sharply changed from 73% cis-1,4-selectivity to 79-99% 3,4-selectivity, and M_n and M_w/M_n were controlled to achieve living nature. The relationship between the coordination role of polar olefins and their regulation and controllability effects over the copolymerization was explained by kinetic studies and DFT calculations.