4.7 Article

Living Coordinative Chain-Transfer Polymerization and Copolymerization of Ethene, α-Olefins, and α,ω-Nonconjugated Dienes using Dialkylzinc as Surrogate Chain-Growth Sites

Journal

MACROMOLECULES
Volume 41, Issue 21, Pages 7829-7833

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/ma801962v

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Highly efficient, rapid, and reversible chain transfer between active transition-metal-based propagating centers derived from {Cp*Hf(Me)[N(Et)C(Me)N(Et)]}[B(C6F5)(4)] (Cp* = eta(5)-C5Me5) (1a) or {Cp*Hf(Me)[N(Et)-C(Me)N(Et)]} [B(C6F5)(3)Me] (1b) and multiple equivalents of diatkylzinc (ZnR2) acting as surrogate chain-growth sites has been achieved for establishing the living coordinative chain-transfer polymerization (CCTP) of ethene, alpha-olefins, and alpha,omega-nonconjugated dienes and living CCTP copolymerization of ethene with alpha-olefins and alpha,omega-nonconjugated dienes. These living CCTP processes not only provide a work-around solution to the one chain per metal cap on product yield currently limiting traditional living coordination polymerization of ethene and alpha-olefins but, in addition, provide access to practical volumes of a variety of unique new classes of precision polyolefins of tunable molecular weights and very narrow polydispersity (M-w/M-n <= 1.1).

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