上海科技大学知识管理系统

["alpha-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 alpha-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 alpha-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 alpha-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 homopolymerization of linear alpha-olefins has been developed. The success of this polymerization relies on the high efficiency of 1,4-cyano group migration. This approach can be applied to homopolymerize alpha- substituted styrenes or acrylates. As a chain transfer agent, a symmetric allylic sulfide is created to regulate the propagating thiyl radicals over the polymerization process. image"]