1070-4272/05/7805-0802C2005 Pleiades Publishing, Inc.
Russian Journal of Applied Chemistry, Vol. 78, No. 5, 2005, pp. 802!805. Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 5,
2005, pp. 818!821.
Original Russian Text Copyright + 2005 by Man’ko, Mel’nichenko, Bovkunenko, Shendrik, Fedoseeva, Goncharov.
AND POLYMERIC MATERIALS
Radical Copolymerization of Fluoroalkyl Methacrylates
with Methyl Methacrylate
K. I. Man’ko, V. I. Mel’nichenko, O. P. Bovkunenko, A. N. Shendrik,
A. A. Fedoseeva, and E. N. Goncharov
Donetsk National University, Donetsk, Ukraine
Received January, 26, 2005
Abstract-Lauryl peroxide initiated radical copolymerization of 1,1,3-trihydroperfluoropropyl methacrylate
and 1,1,5-trihydroperfluoroamyl methacrylate with methyl methacrylate was studied. The kinetic parameters
of copolymerization for these systems were determined at low degrees of conversion. Optically transparent
copolymers with glass transition points within 50380oC were synthesized.
Polymers based on fluorine-containing acrylates
and methacrylates find application in various fields of
industry owing to an advantageous combination of
properties: transparency and weather, thermal, and
chemical resistance, as well as other parameters.
They are used for impregnation of leather, paper, and
textiles for imparting water-, oil-, and mud-repelling
properties to these materials . Because of high oxy-
gen permeability, polyfluoroalkyl (meth)acrylates
were patented as gas-separation membranes .
Optical properties (low refractive indices, high light
transmittance) make these materials suitable for opti-
cal and optoelectronic applications . In this context,
polymerization of fluoroalkyl (meth)acrylates has
recently received much attention [4, 5].
It should also be noted that some properties of
homopolymers (water repellency, cold fluidity, low
glass transition points), as well as high costs of the
initial monomers, limit their application. These draw-
backs can be eliminated to a certain extent by copoly-
merization of fluorinated monomers with vinyl mono-
mers, for example, alkyl methacrylates, styrene, and
methacrylic and acrylic acids. For such systems, it is
urgent to carry out regular kinetic studies and also to
establish the structure3property relationships.
In this work, we studied radical copolymerization
of 1,1,3-trihydroperfluoropropyl methacrylate (F
1,1,5-trihydroperfluoamyl methacrylate (F
methyl methacrylate (MMA) and the physicochemical
properties of the copolymers synthesized.
Copolymerization of F
with MMA was
carried out at 65oC. The monomers were purified by
vacuum distillation in a nitrogen atmosphere. Lauryl
peroxide which served as initiator was purified by re-
precipitation from chloroform into methanol. The
concentration of the initiator was 5 010
of the monomer mixture. The content of the fluori-
nated components in the monomer mixture was varied
from 9.09 to 83.3 mol%. The kinetics of copolymeri-
zation to high conversions were studied gravimetrical-
ly. The copolymers were isolated by reprecipitation
from acetone into methanol. The composition of the
copolymers was determined by IR spectroscopy. As
analytical band served that corresponding to vibrations
of the 3CF
3 groups at 800 cm
. The IR spectra
of the copolymers were recorded on a Specord 75-IR
spectrometer in an acetonitrile solution in KBr cells
with a layer thickness of 0.4 cm. The viscosity of
the monomer mixtures was measured in an Ubbelohde
viscometer. The thermomechanical properties of the
polymers were studied by the method described in .
The water wettability of the polymers at 20oC was
determined by measuring the contact angle . The
time dependences of the conversion of the monomer
(Fig. 1) show that, in the initial stages of copolymeri-
Fig. 1. Variation of the conversion of the monomer S with
the time t at T =65oC. Mixture composition: (1) MMA,
3MMA, and (3)F