Abstract
Abstract Work carried out in the past few years aimed at elucidating the mechanism of initiation of vinyl polymerization when a donor and an acceptor molecule, one or both of which may be vinyl monomers, is summarized. The emphasis of our investigation has been on polymerizable ether donors and strong electron acceptors which do not undergo polymerization, or the acceptor vinylidene cyanide. Alkyl vinyl ethers were polymerized in the presence of tetracyanoquinodimethane (TCNQ) and 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) in polar solvents. Observation of the ESR spectrum of the DDQ radical anion and the isolation of a 1:1 addition product of DDQ and alkyl vinyl ether when the two are mixed in a 1:1 ratio and quenched in alcohol support an initiation mechanism involving a coupling reaction of the donor monomer (radical cation) and the acceptor initiator (radical anion). The reaction of vinylidene cyanide (VC) with the vinyl ethers p-dioxene, dihydropyran, ethyl vinyl ether, isopropyl vinyl ether, and ...
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