ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 9, pp. 1638!1641. + Pleiades Publishing, Ltd., 2008.
Original Russian Text + L.L. Semenycheva, E.I. Bogatova, V.V. Vins, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 9,
AND POLYMERIC MATERIALS
Copolymers of Butyl Acrylate with Vinyl Alkyl Ethers
as Thickening Additives to Oils
L. L. Semenycheva, E. I. Bogatova, and V. V. Vins
Lobachevsky Nizhni Novgorod State University, Nizhni Novgorod, Russia
Sovremennye Khimicheskie Tekhnologii Private Company, Russia
Received December 28, 2007
Abstract-The possibility of preparing copolymers of butyl acrylate with vinyl butyl and vinyl isobutyl
ethers with various ratios of monomeric units by radical polymerization was examined.
Macromolecular compounds are widely used as
depressor and thickening additives to oils [1, 2].
Well-known additives based on polyalkyl methacryl-
ates often exhibit thickening and depressor proper-
ties simultaneously . However, the use of alkyl
acrylates, in particular, polybutyl acrylate, for this
purpose is restricted by their limited solubility in
In this study, as thickeners for dioctyl sebacate
(DOS), which is the base of synthetic oils , we
suggest copolymers of butyl acrylate (BA) with vinyl
isobutyl (ViBE) and vinyl butyl (VnBE) ethers. We
examined the synthesis features and properties of
We used freshly distilled ViBE and VnBE (833
84oC fraction) .
Butyl acrylate was purified by the procedure
described in [7, 10]. The physicochemical constants
of BA are in agreement with published data .
Azobis(isobutyronitrile) (AIBN) was purified by
recrystallization from methanol .
The polymerization was performed at 50oCin
evacuated ampules in the bulk of the monomer. The
ampule was charged with a definite weighed portion
of AIBN and with the comonomers: ViBE (or
VnBE) and BA. The mixture was degassed by re-
peated freezing3pumping3thawing (~10
Polymer samples were purified by reprecipitation
from acetone into ethanol and then dried at reduced
pressure to constant weight. The conversion was
estimated gravimetrically by the dry residue .
The content of BA units in ViBE3BA and VnBE3
BA copolymers was determined by IR spectroscopy.
The composition of ViBE3BA and VnBE3BA co-
polymers was determined from the BA content.
Studies were performed on an Infrolyum-FN-801 IR
spectrometer in KBr cells (layer thickness 0.51 mm).
The content of BA in the copolymer was determined
with a calibration plot from the areas of the charac-
teristic vibration band of the carbonyl group at
The molecular-weight characteristics were deter-
mined by gel permeation chromatography (GPC) on
a Knauer liquid chromatography (Germany) with a
Linear-2 linear column (Phenomenex, USA). An RI
Detector K-2301 differential refractometer was used
as detector, and chloroform was an eluent. The
eluent flow rate was 1 ml min
, and the tempera-
ture, 25oC. For the calibration we used close-cut
polystyrene references .
The kinematic viscosity of solutions of the poly-
mers in DOS was determined with a VPZh-4 vis-
cometer by the standard procedure . The viscos-
ity indexwas calculated by the procedure described
The well-known feature of butyl acrylate polymer
at >30% conversion is low solubility in organic solv-
ents, inculding oils, due to formation of the cross-
linked polymer [16, 17]. To obtain an oil-soluble
additive based on polybutyl acrylate, into BA poly-
mer we introduced units of readily oil-soluble vinyl