Nonionogenic Star-Shaped Calixarenes:
Synthesis and Ionophore Properties
A. V. Ten’kovtsev and A. B. Razina
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Received April 9, 2009
Abstract—New approach to the synthesis of star-shaped polymers based on calixarene with amphiphilic
arms of nonionogenic nature is described. The ionophore properties of the resulting polymer with respect to
ions of alkali metals, europium, and uranium were studied by an example of a polymer containing residues of
ω-cetyloligoethylene oxide as arms.
AND POLYMERIC MATERIALS
ISSN 1070-4272, Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 9, pp. 1615–1619. © Pleiades Publishing, Ltd., 2009.
Original Russian Text © A.V. Ten’kovtsev, A.B. Razina, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 9, pp. 1514–1518.
Amphiphilic star-shaped systems based on
calixarenes are presently an object of intensive
research. On the one hand, this is due to the trend of
systems of this kind toward formation of micelles with
a narrow size distribution, which is of interest for
development of systems for delivery of medicinal
agents. On the other hand, this interest is caused by the
presence of a calixarene ring, which tends to form
complexes with low-molecular-weight compounds and
metal ions . Calix[n]arenes are cyclic oligomers
produced in polycondensation of 4-tert-butylphenol
with formaldehyde , with n determining the number
of phenol residues in a macrocycle. The possibility of
modifying calixarenes along both the upper and lower
rims and varying the macrocycle size resulted in the
synthesis of a wide variety of calixarene derivatives
and in a study of their complex-forming properties .
In doing so, it was shown that introduction of
amphiphilic structural groups and addition of
surfactants to the system enhance the ionophore
properties of the molecules.
Methods for synthesis of star-shaped, including
amphiphilic, calixarene-containing polymers have
been rather well developed [4–7]. In particular,
methods of living polymerization have been used to
obtain star-shaped polymers with arms having the form
of block-copolymers of the acrylic acid–methyl
acrylate  and polyethylene oxide–polystyrene 
types. Despite the considerable advances in the
application of the living radical polymerization, the
synthesis of block-copolymers is limited by the small
number of monomers that can be involved in processes
of this kind. In addition, the ionophore properties
of such macromolecules were almost not studied so
An original approach to the synthesis of calixarene-
containing star-shaped polymers with nonionogenic
arms of amphiphilic nature is based on the
condensation method for synthesis of polymers . In
this case, the role of arms can be played by
commercially available oligoethylene oxides with
hydrophobic terminal groups.
This communication describes the synthesis of an
octafunctional monomer based on calixarene and
the corresponding star-shaped polymer with arms in
the form of ω-cetyloligoethylene oxide (MM 1100) and
presents the results of a study of its ionophore
properties with respect to alkali metal ions.
The scheme of the synthesis of the polymer under
study is presented in Scheme 1.
It is known that one of the main difficulties in
synthesis of star-shaped polymers is the full
functionalization of all groups of a calixarene in the
“from the ring” approach. In this context, of particular
importance in using condensation methods is the