Mechanistic Insight into the Photocontrolled Cationic Polymerization of Vinyl Ethers.

ABSTRACT: The mechanism of the recently reported photocontrolled cationic polymerization of vinyl ethers was investigated using a variety of catalysts and chain-transfer agents (CTAs) as well as diverse spectroscopic and electrochemical analytical techniques. Our study revealed a complex activation step characterized by one-electron oxidation of the CTA. This oxidation is followed by mesolytic cleavage of the resulting radical cation species, which leads to the generation of a reactive cation-this species initiates the polymerization of the vinyl ether monomer-and a dithiocarbamate radical that is likely in equilibrium with the corresponding thiuram disulfide dimer. Reversible addition-fragmentation type degenerative chain transfer contributes to the narrow dispersities and control over chain growth

SUBMITTER: Michaudel Q 

PROVIDER: S-EPMC5806523 | biostudies-literature | 2017 Nov

REPOSITORIES: biostudies-literature