Rare-earth-metal-catalyzed highly 3,4-regioselective polymerization of polar 1-phenyl-1,3-butadiene derivates

Abstract

The incorporation of polar functionalities into non-polar polymers represents a feasible strategy to tailor polymeric properties, and the direct metal-catalyzed coordination (co)polymerization of polar monomers is always a challenging topic. In this study, we have successfully realized the polymerization of 1-phenyl-1,3-butadiene derivates with diverse polar functionalities in catalysis by a rare-earth metal catalytic system, affording highly 3,4-regular polymers (>99% 3,4-) with high molecular weights. Moreover, the copolymerization of 1-(4-fluorophenyl)-1,3-butadiene with 1-phenyl-1,3-butadiene was also smoothly realized, and the composition of the resultant copolymer could be easily tailored by the initial comonomer feed ratio. NMR analysis and kinetic investigation suggested random microstructures of the final copolymers (r_p-FPB = 1.66 and r_1PB = 2.00).