Abstract
The free radical initiation chemistry of highly reactive trialkylboranes (R3B, R = n-butyl), stabilized by complexation to amines (A–R3B), has been investigated using spin trapping methods and electron paramagnetic resonance spectroscopy. Protonation of A–R3B leads to release of R3B and its subsequent autooxidation in the presence of molecular oxygen. This reaction provides highly reactive alkyl and alkoxy radicals for initiation of α–olefin polymerization. Kinetic traces of the R3B autooxidation reaction were obtained by monitoring the relative concentrations of trapped radical species as a function of time for several different initial conditions (acid concentrations). Analysis of a representative kinetic run is discussed in terms of several proposed mechanisms from the literature.
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