ie504550p_si_001.pdf (2.26 MB)
Epoxidation of the Commercially Relevant Divinylbenzene with [tetrakis-(Pentafluorophenyl)porphyrinato]iron(III) Chloride and Its Derivatives
journal contribution
posted on 2015-01-28, 00:00 authored by Kainan Zhang, Ying Yu, SonBinh T. Nguyen, Joseph
T. Hupp, Linda J. Broadbelt, Omar K. FarhaFluorinated Fe-porphyrins,
especially [tetrakis(pentafluorophenyl)porphyrinato]iron(III)
chloride (tetrakis(pentafluorophenyl)porphyrinato
= TPFPP) (TPFPP)FeCl (Fepor-2a), were found to be highly
efficient for catalyzing the double epoxidation
of divinylbenzene (DVB) to divinylbenzene dioxide (DVBDO), a novel
component of epoxy resin formulation. The electronic properties of
the catalysts are highly dependent on the substituents on the phenyl
groups of these metalloporphyrins. The electron-rich fluorinated Fe-porphyrins
are more selective toward epoxidation but are more vulnerable toward
decomposition in H2O2. On the other hand, the
electron deficient Fe-porphyrins are more stable, yet more Lewis acidic,
which facilitates the formation of byproducts such as epoxide ring
opening and overoxidation.