Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 11, pp. 1958−1964.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © L.B. Vaganova, A.V. Maleeva, A.V. Piskunov, D.F. Grishin, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 11,
AND POLYMERIC MATERIALS
Synthesis of Styrene–Methyl Methacrylate Block Copolymers
Using Germanium and Tin Derivatives
Containing a Macroradical
L. B. Vaganova
, A. V. Maleeva
, A. V. Piskunov
, and D. F. Grishin
Research Institute of Chemistry, Nizhni Novgorod State University, Nizhni Novgorod, Russia
Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, Nizhni Novgorod, Russia
Received December 20, 2010
Abstract—Block copolymerization of polystyrene synthesized in the presence of catecholate complexes of Group
IV nontransition elements was studied. The effect of Ge(IV) and Sn(IV) o-semiquinolate derivatives formed in the
course of styrene polymerization on the formation of the macroinitiator of methyl methacrylate polymerization
A particular place in controlled synthesis of macromol-
ecules as one of topical and promising lines in the synthetic
chemistry of polymers in the past decade is occupied by
methods involving the use of transition metal compounds
[1–4]. Numerous papers deal with this problem.
At the same time, with certain ligand surrounding,
nontransition metal compounds in some cases can also
efﬁ ciently control the polymerization of vinyl monomers.
For example, when a nontransition metal complex con-
tains a redox-active ligand, this complex is capable to
participate in oxidative addition and reductive elimination
reactions, showing similar behavior to transition metal
where R is a radical, М is a nontransition metal, Х is an
alkyl ligand or halogen atom, and L is a solvating ligand;
n = 1, 2; m = 1, 2.
Such nontransition metal complexes, in particular,
those with 3,6-di-tert-butylpyrocatechol, show prom-
ise not only as reagents for scavenging radical species
[scheme (1)] with the subsequent product identiﬁ cation
by ESR [5–8], but also as agents controlling polymer-
ization processes that occur by the reversible inhibition
The chain propagation mechanism following the
reversible inhibition pattern, in particular, that involv-
ing organometallic compounds [1–4], suggests that the
polymer isolated in any step can initiate polymerization
of another monomer. The formation of block copolymers
not only directly proves the occurrence of a “living” pro-
cess in homopolymerization, but also allows quantitative
estimation of the contribution of this mechanism to the
overall polymerization process.
The goal of this study is to compare the initiating
power manifested in methyl methacrylate polymerization
by Ge and Sn o-semiquinolate derivatives containing
a polystyrene radical.
As investigation objects we chose catecholate com-
plexes of Group IV metals, solvated by tetrahydrofuran