Transcript The Nitroxides in Polymerization Gilles OLIVE, Christianne Göttgens, Wilfred Smulders, Michael MONTEIRO Laboratory of Polymer Chemistry, Eindhoven Polymer Laboratories, Eindhoven University of Technology, P.

The Nitroxides in Polymerization
Gilles OLIVE, Christianne Göttgens, Wilfred Smulders,
Michael MONTEIRO
Laboratory of Polymer Chemistry, Eindhoven Polymer Laboratories, Eindhoven University of Technology,
P. O. Box 513, 5600 MB Eindhoven, The Netherlands
Aim and Principle :
M
C +
O
N
M
C
O
N
A lk o x y a m in e
The aim is to control the radical polymerization.
M
The principle is the use of a reversible coupling
between the nitroxide and the growing polymeric
chain.
C
How to synthesize them ?
R
 By oxidation of a secondary amine that a no hydrogen
on the carbon close to the nitrogen :
R
N
R
R
[O x]
R
H
N
R
O
R
R
or
+
R
R
R
N
1) YM gX
2) [O x]
R
O
R
R
R
 Spin-trapping of a radical on a nitroso :
R
R
R
R
N
R
R
Y
R
 Addition of a radical or a Grignard on a nitrone :
R
O
Y
R
R
N
O
+
R
Y
N
R
R
Y
O
What can we change ?
N
 The functionality (different groups) :
N
,
O
 The type (linear, cyclic) :
O
N
,
O
N
,
N
O
O
R
 The structure (skeleton different) :
OH
N
O
R
,
R'
N
O
H
R'
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, 5666-5672.