Monomer- and polymer radicals of vinyl compounds: EPR and DFT studies of geometric and electronic structures in the adsorbed state

Electron paramagnetic resonance (EPR) spectroscopy was applied to study the paramagnetic species formed from styrene, 1,1-diphenylethylene, α-methylstyrene, β-methylstyrene and methylmethacrylate adsorbed on amorphous silica gel after γ-irradiation at 77 K. Radicals formed by the hydrogen atom addition at the vinyl group of the monomers were observed in all samples. The hydrogen atoms were shown to originate to a large extent from the adsorbent by using silica gel with deuterated silanol groups. An EPR spectrum assigned to a propagating radical was observed at increased temperature for samples containing methylmethacrylate (MMA). The structures of the adsorption complexes, the respective hyperfine splitting constants and the adsorption energies were calculated by applying DFT quantum chemical methods. The reaction between an MMA molecule and the MMA radical and the structure of the propagating radical was modeled. The calculated hyperfine splitting constants for all radicals confirmed the assignment of the experimental spectra.

H atoms released by irradiation of surface silanol groups initiate radical formation in methylmethacrylate, MMA. The radical attacks an MMA molecule at increased temperature forming a propagating radical identified by EPR.Figure optionsDownload as PowerPoint slideHighlights
► Radicals of vinyl compounds adsorbed on silica gel were studied by EPR.
► Radicals were mainly formed by addition of H atoms originating from silanol groups.
► The radical-surface complexes were theoretically investigated by DFT calculations.
► The formation of a propagating radical observed by EPR was theoretically modeled.