Group Transfer Radical Polymerization for the Preparation of Carbon-Chain Poly(α-olefins)

Radical polymerization is a powerful technique for producing a variety of polymeric materials. However, the chain transfer reaction impedes the formation of polymers from many common α-olefins such as propene and 1-butene using this method. Consequently, poly(α-olefins) are predominantly produced via coordination polymerization. To address this limitation, we have devised a strategy involving group transfer radical polymerization (GTRP) to facilitate the radical homopolymerization to access carbon-chain poly(α-olefins). This novel approach enables the precise construction of a diverse array of carbon-chain poly(α-olefins) with high molecular weights. Furthermore, by utilizing non-conventional monomers, we extend the applicability of this technique to the copolymerization of α-olefins with acrylonitrile, paving the way for the synthesis of sequence-defined copolymers. This research offers an innovative paradigm for the precise synthesis of polymers, potentially pioneering new prospects in the fabrication of high-performance materials.