Organometallic mediated radical polymerization of vinyl acetate with Fe(acac)2.

Authors :: Xue, Zhigang
Poli, Rinaldo
Source :: Journal of Polymer Science. Part A, Polymer Chemistry; Aug2013, Vol. 51 Issue 16, p3494-3504, 11p
Publication Year :: 2013
Abstract: ABSTRACT The radical polymerization of vinyl acetate (VAc) is moderated by iron(II) acetylacetonate (Fe(acac)<subscript>2</subscript>) by the organometallic route (OMRP), as well as by degenerative transfer polymerization (DTP) when in the presence of excess radicals, through the formation of thermally labile organometallic Fe<superscript>III</superscript> dormant species. The poly(vinyl acetate) (PVAc)-Fe<superscript>III</superscript>(acac)<subscript>2</subscript> dormant species has been isolated in the form of an oligomer and characterized by <superscript>1</superscript>H NMR, EPR, and IR methods, and then used as a single-component initiator for the OMRP of VAc. The degree of polymerization of this isolated oligomeric species demonstrates the limited ability of Fe(acac)<subscript>2</subscript>, relative to the Co(acac)<subscript>2</subscript> congener, to rapidly trap the growing PVAc radical chain. Control under OMRP conditions is improved by the presence of Lewis bases, especially PMe<subscript>2</subscript>Ph. On the other hand, iron(II) phthalocyanine inhibits the radical polymerization of VAc completely. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 3494-3504 [ABSTRACT FROM AUTHOR]