1. The Nitroxides in Polymerization
Gilles OLIVE, Christianne Göttgens, Wilfred Smulders,
Michael MONTEIRO
Aim and Principle :
The aim is to control the radical polymerization.
The principle is the use of a reversible coupling
between the nitroxide and the growing polymeric
chain.
How to synthesize them ?
 By oxidation of a secondary amine that a no hydrogen
on the carbon close to the nitrogen :
 Addition of a radical or a Grignard on a nitrone :
 Spin-trapping of a radical on a nitroso :
What can we change ?
 The functionality (different groups) :
 The type (linear, cyclic) :
 The structure (skeleton different) :
Explanation ?
According to Hans Fisher1, by a kinetics analysis of “living” polymerization initiated and controlled by reactions
involving persistent radicals. By this analysis, it was found that a simple self-regulation operates which is known
as the persistent radical effect in the other areas of radical chemistry.
1 H. Fisher, Macromolecules, 1997, 30,