Alkyne Polymers from Stable Butatriene Homologues: Controlled Radical Polymerization of Vinylidenecyclopropanes

18 November 2022, Version 1
This content is a preprint and has not undergone peer review at the time of posting.


Controlled polymerization of cumulenic monomers represents a promising yet underdeveloped strategy towards well-defined alkyne polymers. Here we report a stereoelectronic effect-inspired approach using simple vinylidenecyclopropanes (VDCPs) as butatriene homologues in controlled radical ring-opening polymerizations. While being thermally stable, VDCPs mimic butatrienes via conjugation of the cyclopropane ring. This leads to exclusive terminal-selective propagation that affords a highly structurally regular alkynebased backbone, featuring complete ring-opening and no backbiting regardless of polymerization conditions.


ring-opening polymerization
radical polymerization
controlled polymerization
alkyne polymers

Supplementary materials

supporting information
Procedures, characterizations, GPC traces, NMR spectra, computation details.


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