Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 4, pp. 738−741.
Pleiades Publishing, Ltd., 2010.
Original Russian Text
O.I. Tuzhikov, T.V. Khokhlova, S.N. Bondarenko, S.A. Orlova, E.A. Abramova, 2010, published in Zhurnal Prikladnoi Khimii, 2010,
Vol. 83, No. 4, pp. 686−689.
AND POLYMERIC MATERIALS
Reaction of Di-2-chloroethyl 2-Chloroethanephosphonate
with Potassium Methacrylate
O. I. Tuzhikov
, T. V. Khokhlova
, S. N. Bondarenko
, S. A. Orlova
, and E. A. Abramova
Volgograd State Technical University, Volgograd, Russia
Volzhskii Polytechnic Institute, Volzhskii, Volgograd oblast, Russia
Received June 24, 2009
Abstract—Reaction of di-2-chloroethyl 2-chloroethanephosphonate with potassium methacrylate at various
component ratios was studied with the aim to prepare products containing methacrylate and vinyl functional
groups. The structures of the compounds obtained were examined by
H NMR and IR spectroscopy and by gas
Synthesis of phopshorus- and halogen-containing
oligoester acrylates used as modiﬁ ers in preparation of
ﬁ reproof composite polymeric materials was the subject
of numerous studies [1–5]. Thermal polycondensation
of 2-haloalkyl phosphates was examined, the reaction
products were identiﬁ ed, and their characteristics were
determined [1–4]. Bakhtina et al.  studied the reaction
of dimethyl methanephosphonate with dichloroethane,
trichloropropane, and dichlorodiethyl ether in the
presence of catalysts at 120–250°С. The resulting
phosphorus-containing oligomers were suggested for
use both in the individual form (as protective coatings)
and as ﬁ llers for a wide range of polymers.
Further development of studies in this ﬁ eld seems
promising in the context of diverse speciﬁ c requirements
imposed on polymeric materials. Previous studies [6–9]
showed that it is appropriate to examine polyfunctional
organophosphorus acids with two or more polymerization-
capable methacrylic groups. These compounds can be
prepared from an available commercial product, di-2-
This study deals with the synthesis of 2-chloro-
ethanephosphonic acid esters by the reaction of di-2-
chloroethyl 2-chloroethanephosphonate with a meth-
acrylic acid salt at various component ratios.
Di-2-chloroethyl 2-chloroethanephosphonate I
was prepared by isomerization of tri-2-chloroethyl
phosphite on heating. As methacrylic acid derivative
we used its potassium salt II. The reaction of I with II
was performed at 120–140°С in dimethylformamide.
To isolate the reaction products, the KCl precipitate
formed in the process was ﬁ ltered off, and the solvent
was evaporated from the ﬁ ltrate in a vacuum. The
composition and structure of the synthesized products
were conﬁ rmed by IR and
H NMR spectroscopy and
by gas chromatography–mass spectrometry (GC–MS).
Н NMR spectra of substances (CDCl
were recorded with a Varian Mercury-300 spectrometer
operating at 300 MHz, internal reference HMDS; the
IR spectra were taken on a Specord M-82 spectrometer.
GC–MS measurements were performed with a Perkin–
Elmer Clarus 500 device equipped with an MSD. The
chromatographic separation was performed under the
following conditions. Vaporizer temperature 260°С,
initial column temperature 100°С. After 50 s, the
column temperature was raised to 220°С at a rate of
15 deg min
, after which it was raised to 305°C at a rate
of 8 deg min
. Column length 25 m, diameter 0.2 mm.
Stationary phase Elite-17 MS, carrier gas He.