TY - JOUR
T1 - Expanding the alternating propagation-chain transfer-based polymerization toolkit
T2 - the iodo-ene reaction
AU - Scott, Timothy F.
AU - Furgal, Joseph C.
AU - Kloxin, Christopher J.
PY - 2015/12/15
Y1 - 2015/12/15
N2 - Analogous to the thiol-ene and phosphane-ene polymerizations, radical-mediated iodo-ene reactions are described here that proceed via alternating propagation and chain transfer (i.e., APT) reactions between perfluoroiodide- and vinyl-bearing monomers. The thermal polymerization of a diiodo/tetraene formulation yielded a cross-linked, homogeneous polymer that was approximately seven times as radiopaque as aluminum owing to its high iodine content. Visible-light photopolymerizations of model iodo-ene monomers were monitored using mid-IR spectroscopy, revealing that the perfluoroiodide functional group consumption exceeded that of the vinyl, a discrepancy that decreased with increasing irradiation intensities and hence polymerization rates. The functional group conversions in resin formulations with a large initial perfluoroiodide excess exacerbated secondary side reactions that led to off-stoichiometric functional group consumption; nevertheless, photopolymerization of resin formulations with excess vinyl stoichiometry proceeded according to the ideal APT mechanism.
AB - Analogous to the thiol-ene and phosphane-ene polymerizations, radical-mediated iodo-ene reactions are described here that proceed via alternating propagation and chain transfer (i.e., APT) reactions between perfluoroiodide- and vinyl-bearing monomers. The thermal polymerization of a diiodo/tetraene formulation yielded a cross-linked, homogeneous polymer that was approximately seven times as radiopaque as aluminum owing to its high iodine content. Visible-light photopolymerizations of model iodo-ene monomers were monitored using mid-IR spectroscopy, revealing that the perfluoroiodide functional group consumption exceeded that of the vinyl, a discrepancy that decreased with increasing irradiation intensities and hence polymerization rates. The functional group conversions in resin formulations with a large initial perfluoroiodide excess exacerbated secondary side reactions that led to off-stoichiometric functional group consumption; nevertheless, photopolymerization of resin formulations with excess vinyl stoichiometry proceeded according to the ideal APT mechanism.
UR - http://www.scopus.com/inward/record.url?scp=84949908067&partnerID=8YFLogxK
U2 - 10.1021/acsmacrolett.5b00640
DO - 10.1021/acsmacrolett.5b00640
M3 - Article
AN - SCOPUS:84949908067
VL - 4
SP - 1404
EP - 1409
JO - ACS Macro Letters
JF - ACS Macro Letters
SN - 2161-1653
IS - 12
ER -