In recent years, the study of radical polymerization has gone through something of a renaissance. This has seen significant changes in our
understanding of tbe area and has led to major advances in our ability to control
and predict the outcome or polymerization processes. Two major [actors may be
judged responsible for bringing this about and for spurring an intensified interest
in all aspects of radical chemistry:
Firstly, the classical theories on radical reactivity and polymerization
mechanism do not adequateJy explain the rate and specificity of simpJe radical
reactions. As a consequence, they can not be used Lo predict the manner in which
polymerization fate parameters and details of polymer microstructurc depend on
reaction conditions, conversion and molecular weight distribution,
Secondly, new techniques have been developed vvhich allow a more detailed
characterization of both polymer microstructures and the kinetics and mechanism
of polymerizations. Ihis has allowed mechanismstructureproperty relationships
to bc more rigorOllsly established.
The new knowledge and understanding of radical processes has resulted in
new polymer structures and in new routes to estabJished matel'ials; many with
commercial significance. For example, radical polymerization is now used in the
production of block copolymers, Darrow polydispcrsity homopolymcrs, and othcr
materials or controlled architeclure that were previously available only by more
demanding routes. These commercial developments have added to the resurgence
of studies on radical polymcrization.