Flexible “Sandwich” (8-Alkylnaphthyl α-Diimine) Catalysts in Insertion Polymerization
You Ge, Shuaikang Li, Weigang Fan, Shengyu Dai
Abstract
8-Arylnaphthyl substituents are privileged motifs frequently integrated into late-transition-metal catalysts, endowing them with an ability to retard chain transfer in ethylene polymerization. In this contribution, we disclose a sort of novel α-diiminenickel and -palladium complexes containing flexible 8-alkylnaphthyl in lieu of rigid 8-arylnaphthyl and their catalytic performance in ethylene polymerization. An interesting feature of these 8-alkylnaphthyl-substituted α-(diimine)PdMeCl complexes is that they present as a mixture of syn and anti isomers (syn:anti = ca. 1:1 ratio, determined by 1H and 13C NMR spectroscopy). In ethylene polymerization, these nickel complexes displayed high activity (up to 3.37 × 106 g mol–1 h–1) and generated branched polyethylenes with broad or bimodal molecular weight distributions (4.6–29.3), while the corresponding palladium complexes exhibited moderate activity, producing highly branched polyethylenes with unimodal and narrow molecular weight distributions (<1.8). In ethylene (E)/methyl acrylate (MA) copolymerization, highly branched E-MA copolymers with considerable MA incorporations were achieved by these palladium complexes. Most interestingly, compared to rigid 8-arylnaphthyl-substituted α-diiminenickel and -palladium complexes, the flexible 8-alkylnaphthyl ones showed significantly improved activity and generated lower or comparable molecular weight polyethylenes or E-MA copolymers.