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Xanthate Mediated Living Polymerization of Vinyl Acetate: A Systematic Variation in MADIX/RAFT Agent Structure

✍ Scribed by Martina H. Stenzel; Lyndal Cummins; G. Evan Roberts; Thomas P. Davis; Philipp Vana; Christopher Barner-Kowollik


Publisher
John Wiley and Sons
Year
2003
Tongue
English
Weight
146 KB
Volume
204
Category
Article
ISSN
1022-1352

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✦ Synopsis


Abstract

Eight xanthates were synthesized to induce living free radical polymerization of vinyl acetate. Four compounds, methyl (4‐methoxyphenoxy)carbonothioylsulfanyl acetate, methyl (methoxycarbonothioyl)sulfanyl acetate, methyl (ethoxycarbonothioyl)sulfanyl acetate and methyl (isopropoxycarbonothioyl)sulfanyl acetate were identified as suitable MADIX/RAFT agents, yielding low polydispersity (PDI < 1.2) poly(vinyl acetate) of molecular weights exceeding 5 × 10^4^ g · mol^−1^. All suitable MADIX/RAFT agents exhibited extended periods of inhibition (0.3 h < t~inh~ < 10 h) and moderate rate retardation. The ability of these compounds to control vinyl acetate polymerization can be correlated with the electron density on the central carbon atom of the xanthate. Electrospray ionization mass spectrometric analysis was performed to complete the investigation on the new MADIX/RAFT agents.

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