Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 5, pp. 777−781.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © D.V. Nesterov, L.S. Molochnikov, M.I. Kodess, E.G. Matochkina, O.V. Koryakova, Yu.G. Yatluk, A.V. Pestov, 2013, published in
Zhurnal Prikladnoi Khimii, 2013, Vol. 86, No. 5, pp. 830−834.
AND POLYMERIC MATERIALS
Synthesis of Poly[N-(2,3-dihydroxypropyl)aminostyrene],
a New Sorbent for Boron(III) Ions
D. V. Nesterov
, L. S. Molochnikov
, M. I. Kodess
, E. G. Matochkina
, O. V. Koryakova
Yu. G. Yatluk
, and A. V. Pestov
Ural State Forestry University, Yekaterinburg, Russia
Postovskii Institute of Organic Synthesis, Ural Division, Russian Academy of Sciences, Yekaterinburg, Russia
Received April 1, 2013
Abstract—A procedure was developed for preparation of poly[N-(2,3-dihydroxypropyl)aminostyrene] via
successive stages of nitration, reduction, and glycidol treatment of polystyrene, which gives the polymer with
a maximal degree of functionalization. The composition and structure of the intermediates and end products of
the polymer-analogous reactions were characterized by elemental analysis, IR spectroscopy, and solid-state
NMR spectroscopy. The sorption characteristics of poly[N-(2,3-dihydroxypropyl)aminostyrene] toward boron-
containing ions were assessed.
Functionalization of macromolecular compounds by
polymer-analogous transformations is recognized as a
powerful tool for broadening the range of practically
important properties of well-known and available
polymeric materials and, consequently, of their
applications. Polystyrene is a polymeric matrix material
commonly used for efﬁ cient preparation of ion-exchange
resins [1–3]. In the case of boron-binding sorbents,
in particular of those based on polystyrene, there is a
need in introducing vicinal hydroxy groups onto the
polymeric matrix to promote formation of tetracoordinate
chelate complexes of boron . Indeed, the existing, in
particular commercial sorbents of boric acid contain
polyatomic alcohol residues attached to the polymer
matrix based on polystyrene [5–11], polyallylamine
, polyethyleneimine [13, 14], chitosan [15–17], and
polymethacrylic acid [18–20]. A drawback suffered by the
last-named matrix is low stability of sorbents on its basis
under acidic and alkaline conditions, for which reason
they have a very limited application within a narrow pH
range and cannot be regenerated for reuse.
Here, we synthesized poly[N-(2,3-dihydroxypropyl)
aminostyrene] (PHAS), a new polystyrene-based sorbent
containing vicinal hydroxy groups, and characterized its
sorption properties toward boron-containing ions.
We used linear polystyrene with molecular weight of
400 kDa (AlfaAesar) and glycidol (Sigma-Aldrich, 99.0%)
without further puriﬁ cation. Tin(II) chloride dihydrate
was recrystallized from water. Polyaminostyrene was
sonicated in a Sonopuls HD 3200 ultrasonic homogenizer
at the working frequency of 20 kHz. The degrees
of nitration, reduction, and hydroxyalkylation were
calculated on the basis of the data of C,H,N-analysis
which was performed on a Perkin-Elmer automatic
analyzer. The degree of substitution with vicinal diol
groups was determined by the known technique .
The diffuse reﬂ ection IR spectra were measured on a
Perkin-Elmer Spectrum-One spectrometer. The solid-
state cross-polarization magic angle spinning (CP/MAS)
C NMR (126 MHz) spectra were recorded on a Bruker
AVANCE-500 spectrometer (rotor diameter 4 mm; spin-
ning rate 5000 Hz).
The polystyrene nitration reaction was carried out