Radical Homopolymerization of Linear α-Olefins Enabled by Cyano Group Migration

16 November 2023, Version 1
This content is a preprint and has not undergone peer review at the time of posting.

Abstract

α-Olefins are valued and abundant building blocks from fossil resources. They are widely used to provide small-molecule or polymeric products. Poly-α-olefins are predominately synthesized via coordination polymerization. Despite numerous advantages of radical polymerization, it has been well-documented as textbook knowledge that α-olefins and their functionalized derivatives cannot be radically homopolymerized because of the degradative chain transfer side reactions. Herein, we report our studies on the homopolymerization of thiocyanate functionalized α-olefins enabled by cyano group migration under radical conditions. By this approach, a library of ABC sequence-controlled polymers with high molecular weights can be prepared. We can also extend this strategy to the homopolymerization of α-substituted styrenic and acylate monomers which are known to be challenging to achieve. Overall, the demonstrated functional group migration radical polymerization could provide new possibilities to synthesize polymers with unprecedented main chain sequences and structures, which are promising candidates for novel polymeric materials.

Keywords

ABC sequence regulated polymers
Radical homopolymerization of α-Olefins
cyano group migration

Supplementary materials

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Title
Radical Homopolymerization of Linear α-Olefins Enabled by Cyano Group Migration
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Supporting Information
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