Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 1, pp. 109−114.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
M.P. Sokolova, S.V. Bronnikov, T.E. Sukhanova, A.I. Grigor’ev, A.Ya. Volkov, G.N. Gubanova, A.A. Kutin, A. Farcas, M. Pinteala,
V. Harabagiu, B. Simionescu, 2010, published in Zhurnal Prikladnoi Khimii, 2010, Vol. 83, No. 1, pp. 112−117.
AND POLYMERIC MATERIALS
Structure, Morphology, and Thermal Properties
of Polyrotaxanes Based on Calixarene
and Modiﬁ ed Polydimethylsiloxane
M. P. Sokolova
, S. V. Bronnikov
, T. E. Sukhanova
, A. I. Grigor’ev
A. Ya. Volkov
, G. N. Gubanova
, A. A. Kutin
, A. Farcas
, M. Pinteala
, and B. Simionescu
Institute of Macromolecular Compounds, Russian Academy of Sciences, St. Petersburg, Russia
Petru Poni Institute of Macromolecular Chemistry, Romanian Academy, Iaşi, Romania
Received August 20, 2009
Abstract—New supramolecular inclusion complexes, polyrotaxanes derived from p-tert-butylcalixarene and
polydimethylsiloxane modified with terminal epoxy groups, were synthesized and studied. The dependence of
the structure, morphology, and thermal properties of polyrotaxanes on the molecular weight of the linear polymer
Supramolecular chemistry, a new ﬁ eld of science
whose principles have been developed by Lehn , attracts
active researchers’ interest. Supramolecular compounds
are systems that consist of different molecules capable of
self-organization, i.e., of spontaneous formation of deﬁ nite
structures by self-assembling of components to form
ensembles differing in properties from the components.
Among supramolecular compounds, a particular place
is occupied by inclusion complexes, rotaxanes ,
formed by host and guest molecules. According to the
designations accepted in the literature, cyclic molecules
having an internal cavity are termed hosts. This cavity
can incorporate a linear guest molecule and retain it by
formation of noncovalent (van der Waals, dispersion,
hydrogen, etc.) bonds. The best studied rotaxanes
are linear polyrotaxanes (PRots) built of macrorings
threaded on linear polymeric macromolecules [3, 4].
In such compounds, the hosts are macrocycles of both
natural (cyclodextrins, CDs) and synthetic (crown ethers,
calixarenes) origins [3–9].
Calixarenes are cyclic p-substituted phenol–
formaldehyde oligomers that consist of phenolic
fragments linked by methylene bridges [10–13]. The
number of structural fragments in calixarenes can
vary from 3 to 20. Owing to unique physicochemical
properties, the calixarene application area is very broad.
They are used as sensors for selective binding of metal
ions, as extractants, as catalytic systems, and for the
development of nonlinear optical devices [10–13].
Most frequently PRots are prepared from calixarenes
with four (calixarene), six (calixarene), and eight
(calixarene) arene fragments in the macroring. The
internal diameter of the cavitiy of these calixarenes is
3.0, 7.6, and 11.7 Å, respectively . The internal cavity
of calixarenes formed by phenolic rings and surrounded
by hydroxy groups is hydrophobic, whereas the external
surface is hydrophilic.
Although PRots formed by calixarenes have been
reported, data on them are not so extensive as those
on PRots with CDs and crown ethers as hosts [3, 4].
For example, Yu et al.  described the synthesis and
physicochemical properties of PRots consisting of
25,27-bis(polyethylene glycol)calix arene and phenol
palmitate. PRots based on p-tert-butylcalixarene and
polyethylene glycol were prepared, and their structure
and thermal properties were studied by NMR and IR