Russian Journal of Applied Chemistry, 2009, Vol. 82, No. 1, pp. 123−127.
Pleiades Publishing, Ltd., 2009.
Original Russian Text
N.K. Kobyakova, M.V. Kuz’mina, E.P. Beshenova, L.N. Beloded, 2009, published in Zhurnal Prikladnoi Khimii, 2009, Vol. 82, No. 1,
AND POLYMERIC MATERIALS
Development of the Conditions of Synthesis of p-Chlorophenyl
Methacrylate of the Desired Purity Grade
N. K. Kobyakova, M. V. Kuz’mina, E. P. Beshenova and L. N. Beloded
Polymers Research Institute, Dzerzhinsk, Nizhni Novgorod oblast, Russia
Received November 1, 2008
Abstract—The process of synthesis of p-chlorophenyl methacrylate by the reaction of p-chlorophenol with
methacryloyl chloride was developed, identification and quantitative determination of admixtures in the targeted
compound was carried out. The optimal conditions of the synthesis for obtaining the high quality monomer were
In the recent years increased the interest to organic
glasses based on the methyl methacrylate (co)polymers
with enhanced thermal stability and low water absorption
that provides their reliable and prolonged exploitation
under various conditions. Such glasses ﬁ nd application
ﬁ rst of all in aviation and also in electrical engineering
and car building industry [1, 2]. As (co)monomers
for the modiﬁ cation of polymethyl methacrylate the
most promising are the methacrylic esters with bulky
cyclic fragments . A special interest is paid to the
methyl methacrylate coplymers with p-chlorophenyl
methacrylate owing to high optical and strength
characteristics, alongside enhanced thermal stability and
low hygroscopicity . However, it has been shown that
when the p-chlorophenyl methacrylate is even slightly
contaminated its physical and optical properties decrease,
e.g., falls thermal stability due to plasticizing effect and
appear optical defects like the glass turbidity. Hence, for
producing organic glass with required set of properties
a modifying monomer of high purity grade should be
synthesized and used.
Unfortunately only scarce information was published
so far on the synthesis of chloro-substituted phenyl
methacrylates [4, 5]. It was only reported that reaction
of p-chhlorophenol with methacryloyl chloride leads to
p-chlorophenyl methacrylate with the yield 53% or less.
The data on the content of contaminants in the ester and
on their inﬂ uence on the optical and physico-mechanical
properties of the polymeric materials were not reported.
The absence of the data on the features of manufacturing
the high purity p-chlorophenyl methacrylate restricts the
control over the synthesis and the possibility of optimal
The aim of this investigation is development of the
method of p-chlorophenyl methacrylate synthesis with
the minimal content of contaminants.
The IR spectra were registered on a Specord М82
instrument in the region of 4000–400 cm
from thin ﬁ lms.
The NMR spectroscopic investigations were carried out
on a DРХ-200 instrument with operating frequency
200 MHz for protons and 50 MHz for the
The samples were dissolved in deuterochloroform form
Aldrich, internal reference TMS.
Chromatographic analysis was carried out on a gas
chromatograph Сhrom-5 with the flame ionization
detector and glass column 2.5 m long and 3 mm in diam-
eter, stationary phase Chromosorb WAW (0.16–0.20 mm)
with 8% of poly(ethylene glycol)adipinate and 2% of
; the column temperature 170°C, the evaporator
temperature 220°C, the hydrogen and nitrogen ﬂ ow rate
30 ml min
. Calculation of the content of contaminants
was performed using internal reference method, as the
reference was used dimethyl succinate.
Methacrylic acid (TU 6-02-917-79, supplement 1),
p-chlorophenol (TU 6-09-4935-80), organic solvents
and other chemicals were corresponding to the technical
documentation and were not puriﬁ ed additionally.