Polymerization, grafting and adsorption in the presence of inorganic substrates: Thermal polymerization of styrene with untreated and γ-irradiated silica gel as a case study

The search for innovative and well-defined organic–inorganic hybrid materials demands that the interplay between polymerization reactions, chemical reactivity, and physical adsorption be fully understood. We examine the case study of the thermal polymerization of styrene in the presence of silica, and the effect of pre-irradiation of silica with γ-rays. The effect of adsorption of styrene-derived radical species on the silica support and polymerization conditions on free and grafted (unextractable) polystyrenes and on polymerization mechanism is discussed on the basis of previous literature findings and new data. Evidence is provided of silica derivatization with various species besides polystyrene (13C CPMAS NMR), including products from a β-scission of the adsorbed radical intermediates ensuing oxygen donation from the silica network. The polymerization mechanism can be cationic as well as radical, depending on reaction conditions, and the cationic route prevails in the grafting of polystyrene from silica, resulting in a bimodal molecular weight distribution.