Origin of Suppressed Chain Transfer in Phosphinephenolato Ni(II)-Catalyzed Ethylene Polymerization.

ABSTRACT: Recent breakthroughs in the generation of polar-functionalized and more sustainable degradable polyethylenes have been enabled by advanced phosphinephenolato Ni(II) catalysts. A key has been to overcome this type of catalysts' propensity for extensive chain transfer to enable formation of high-molecular-weight polyethylene chains. We elucidate the mechanistic origin of this paradigm shift by a combined experimental and theoretical study. Single-crystal X-ray structural analysis and cyclic voltammetry of a set of six different catalysts with variable electronics and sterics, combined with extensive pressure reactor polymerization studies, suggest that an attractive Ni-aryl interaction of a P-[2-(aryl)phenyl] is responsible for the suppression of chain transfer. This differs from the

SUBMITTER: Lin F 

PROVIDER: S-EPMC10755696 | biostudies-literature | 2023 Dec

REPOSITORIES: biostudies-literature