Radical Homopolymerization of Linear α-Olefins Enabled by 1,4-Cyano Group Migration.

α-Olefins are valued and abundant building blocks from fossil resources. They are widely used to provide small-molecule or polymeric products. 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 1,4-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. These polymers are promising candidates for novel polymeric materials.

Radical chemistry in polymer science: an overview and recent advances.

Radical chemistry is one of the most important methods used in modern polymer science and industry. Over the past century, new knowledge on radical chemistry has both promoted and been generated from the emergence of polymer synthesis and modification techniques. In this review, we discuss radical chemistry in polymer science from four interconnected aspects. We begin with radical polymerization, the most employed technique for industrial production of polymeric materials, and other polymer synthesis involving a radical process. Post-polymerization modification, including polymer crosslinking and polymer surface modification, is the key process that introduces functionality and practicality to polymeric materials. Radical depolymerization, an efficient approach to destroy polymers, finds applications in two distinct fields, semiconductor industry and environmental protection. Polymer chemistry has largely diverged from organic chemistry with the fine division of modern science but polymer chemists constantly acquire new inspirations from organic chemists. Dialogues on radical chemistry between the two communities will deepen the understanding of the two fields and benefit the humanity.