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Issue 10, 2012
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Cobalt-mediated radical (co)polymerization of vinyl chloride and vinyl acetate

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The cobalt mediated radical polymerization (CMRP) of vinyl chloride (VC) in the presence of bis(acetylacetonato)cobalt(II) (Co(acac)2) as a controlling agent is presented for the first time. Using an alkyl-Co(III) compound (R0–(CH2–CHOAc)<4–Co(acac)2; R0 = (H3C)2(OCH3)C–CH2–C(CH3)(CN)–) as an initiator, the bulk polymerization under non-isotherm conditions is controlled. 1H NMR spectra of the resulting PVC show that the CMRP process does not significantly affect the level of defects compared to a PVC prepared by a conventional free radical polymerization at the same temperature. Using the same alkyl-cobalt(III) compound, the copolymerization of VC and VAc is controlled at 40 °C provided that enough VAc (about 40 mol%) is present in the polymerization medium to moderate the VC polymerization. In line with reactivity ratios, VC is preferentially incorporated in the polymer at the early stages of the polymerization, leading to copolymers with a high VC content at moderate conversions. This is the first report of a CMRP of VC and of the synthesis of well-defined statistical PVC-co-PVAc copolymers by this technique.

Graphical abstract: Cobalt-mediated radical (co)polymerization of vinyl chloride and vinyl acetate

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Publication details

The article was received on 13 Jun 2012, accepted on 17 Jul 2012 and first published on 18 Jul 2012

Article type: Paper
DOI: 10.1039/C2PY20413D
Polym. Chem., 2012,3, 2880-2891

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    Cobalt-mediated radical (co)polymerization of vinyl chloride and vinyl acetate

    Y. Piette, A. Debuigne, C. Jérôme, V. Bodart, R. Poli and C. Detrembleur, Polym. Chem., 2012, 3, 2880
    DOI: 10.1039/C2PY20413D

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