Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 12, pp. 2021−2028.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © D.F. Grishin, I.D. Grishin, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 12, pp. 1937−1945.
Controlled Radical Polymerization: Prospects
for Application for Industrial Synthesis of Polymers
D. F. Grishin and I. D. Grishin
Research Institute of Chemistry, Lobachevskii State University, Nizhni Novgorod, Russia
Received April 28, 2011
Abstract—Existing methods for polymerization in the “living” chain mode are brieﬂ y analyzed and opportunities
for its use for synthesis of polymeric materials under industrial conditions are considered. Particular examples
of application of radical polymerization in manufacture of homo- and copolymers are given, and prospects for
development of basic and applied research in this topical area of polymeric chemistry in the nearest years are
Controlled radical polymerization (CRP) under
radical-initiation conditions belongs to priority areas in
the development of the synthetic chemistry of polymers
of the last years [1–5]. This is primarily due to the fact
that it can provide a reliable control over the molecular-
mass characteristics of polymers being synthesized and
opens up wide prospects in molecular design, including
the possibility of obtaining hybrid nanosize polymeric
structures. It is no coincidence that about 15 thousand
papers have been published in the last 15 years and more
than 200 patents have been obtained.
A huge interest is exhibited by the scientiﬁ c
community in the area mentioned above, and the
classical free-radical polymerization is widely applied in
industrial polymer syntheses (several tens of millions of
tons annually). It seems, at ﬁ rst sight, somewhat strange
on this background that the number of the presently
implemented technological developments on the basis
of CRP is rather limited.
The review considers certain particular examples
of practical application of CRP methods in industrial
syntheses of polymeric materials and analyzes prospects
for development of basic and applied research in this
exclusively topical area of polymer chemistry.
SPECIFIC FEATURES OF POLYMERIZATION
IN THE “LIVING” CHAIN MODE
In contrast to the classical free-radical polymerization,
the controlled radical polymerization replaces the
quadratic chain termination (interaction of two growing
) with a reversible reaction of
the growth radical with initiator fragments or a special
). This reaction yields a macromolecule
with a labile terminal group (~P
–X), which can readily
dissociate at the resulting bond under the action of heat
or radiation or in interaction with another active species.
The initial macroradical is regenerated and continues
the chain growth:
, and k
are the rate constants of the
corresponding reactions; and M stands for the monomer
In addition, the growing macroradicals may be
involved in a reversible chain transfer, which also results
in that the process occurs in the “living” chain mode: