Russian Journal of Applied Chemistry, 2012, Vol. 85, No. 11, pp. 1676−1680.
Pleiades Publishing, Ltd., 2012.
Original Russian Text © P.A. Demidov, I.A. Lavrent’ev, V.V. Potekhin, 2012, published in Zhurnal Prikladnoi Khimii, 2012, Vol. 85, No. 11, pp. 1766−1770.
AND INDUSTRIAL ORGANIC CHEMISTRY
Reaction of Methyl Acrylate with N,N-Dimethylethanolamine
in the Presence of a Titanium Alkoxide
P. A. Demidov
, I. A. Lavrent’ev
, and V. V. Potekhin
St. Petersburg State Institute of Technology (Technical University), St. Petersburg, Russia
“Khimtek Inzhiniring” Closed Joint-Stock Company, St. Petersburg, Russia
Received July 26, 2012
Abstract—The kinetic features were examined for transesteriﬁ cation of methyl acrylate with N,N-dimethyletha-
nolamine in the presence of tetra(N,N-dimethylaminoethyl) titanate at different molar ratios of the reactants and at
temperatures within 50–80°C, as well as for side reactions of Michael addition at 95–125°C. The major parameters
governing the selectivity of the synthesis of N,N-dimethylaminoethyl acrylate were determined.
N,N-Dimethylaminoethyl acrylate (DMAEA), the
product of transesteriﬁ cation of methyl acrylate with
dimethylethanolamine (DMEA), serves as a raw material
in synthesis of water-soluble polymers having broad-
spectrum applicability (as ﬂ occulants, fragrances, and
The DMAEA synthesis reaction involves an equilib-
rium process and, consequently, requires withdrawing
the resultant methanol from the reaction medium for the
equilibrium to be shifted towards the target product.
Commercially, the transesteriﬁ cation reaction is con-
ducted in an ester production apparatus, comprised of a
continuously stirred tank reactor coupled with a rectifying
column which receives the gas stream to be separated
from methanol, at elevated temperatures (100–140°C),
atmospheric or reduced pressure (40–80 kPa), in the
presence of a homogeneous catalyst and a polymerization
inhibitor. The initial methyl acrylate is used in a 2–3-fold
molar excess with respect to DMEA [1–3].
As known , transesteriﬁ cation of methyl acrylate
with DMEA involves, along with the main reaction of
DMAEA formation, side Michael reactions (addition
of alcohols at the vinyl group). The selectivity of the
process is governed primarily by the choice of catalysts,
among which neutral catalysts, organotitanium [5, 6] and
organotin [1, 3] compounds, have received widespread
application. The kinetic features and mechanism of trans-
esteriﬁ cation of methyl acrylate with DMEA in the pres-
ence of titanium alkoxides have not yet been examined.
Here, we report results that can aid in further optimization
of the reactor design and operation.
We used methyl acrylate [99.7%, TU (Technical Speci-
ﬁ cations) 2435-003-52470063–2003], DMEA (99.3%,
TU 2423-004-78722668–2010), DMAEA (99.9%,
Arkema), methanol [99.5%, GOST (State Standard)
6995–77], and titanium tetraisopropylate (99.7%, TU
2423-008-50284764–2006]. The catalyst was prepared by
the technique described in . For synthesis of Michael
adducts we used the procedure from .
The reactions were carried out in a metal reactor
equipped with a jacket, a thermometer, a stirrer, and a
sampler. Temperature control was achieved via circulation
of the coolant (PMS-100 silicone ﬂ uid) through the reac-
tor jacket and a LOIP LT-300 thermostatic bath. All the
starting chemicals, including the inhibitor (phenothiazine,
0.2%), were introduced into the reactor and heated to the
desired temperature; the warm-up period was no longer
than 5 min. In the transesteriﬁ cation experiments, the
catalyst was introduced into the reaction mixture heated
to the desired temperature; prior to analysis, the catalyst
was removed from the transesteriﬁ cation samples by
precipitation as hydrous titania, and this was followed
by ﬁ ltration of the solution.