The dynamics and yields of peroxide‐initiated grafting of vinyltriethoxysilane (VTEOS) to tetradecane and linear low density polyethylene (LLDPE) are described. VTEOS grafting kinetics at 160°C abide by the basic tenets of radical‐mediated additions in terms of the influence of initiator loading and homolysis rate. However, reaction yields recorded for both the model and polymer systems are surprisingly insensitive to temperature, in apparent conflict with conventional models of free radical addition chemistry. These experimental observations are used to identify the predominant reactions within a general kinetic scheme, and to support the assumptions required to develop a rate expression that captures the effect of reagent concentrations on the dynamics of graft‐modification. POLYM. ENG. SCI. 46:1754–1761, 2006.
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