Synthesis of spin labelled silica and EPR molecular dynamics study at silica–polymer interfaces

Information concerning the interface structure in filler/polymer composites is of key importance for the rationalization of reaction mechanisms in mechano-chemical (extrusion, blending, etc.), thermal or radiation induced free radical processes and for elucidating the factors underlying the reinforcing mechanism. The analysis of the chain dynamics is a suitable tool for undertaking such investigations because any reactivity parameter (rate constants, collisional frequencies, activation energies) and bonding interactions are strictly related to the mobility of the interacting centres. EPR spectroscopy coupled with specific spin labelling at the filler/polymer interface is a tool for making such novel perspective available. In this work, a spin labelling study of the molecular motion at the filler–rubber interface in a silica–SBR blend is reported. Spin labels of different length, spanning a 9–11 Å depth and linked to the surface of silica particles, were prepared and used for determining the rotational diffusion tensors, the T50 and order parameter in silica/SBR interfaces. The measurements carried out as a function of the temperature in comparison with unbound spin probes dispersed in the rubber matrix have afforded information consistent with the structure of the interfaces predicted by molecular–level theoretical models.