ISSN 1070-4272, Russian Journal of Applied Chemistry, 2014, Vol. 87, No. 7, pp. 881−886. © Pleiades Publishing, Ltd., 2014.
Original Russian Text © D.V. Orekhov, O.A. Kazantsev, A.P. Sivokhin, T.A. Khokhlova, 2014, published in Zhurnal Prikladnoi Khimii, 2014, Vol. 87, No. 7, pp. 888−893.
ORGANIC SYNTHESIS AND INDUSTRIAL
Synthesis of Sodium Allyl Sulfonate in an Aqueous
Medium by Micellar Catalysis with Methoxy
Polyethylene Glycol Methacrylates
D. V. Orekhov
, O. A. Kazantsev
, A. P. Sivokhin
and T. A. Khokhlova
Alekseev State Technical University, ul. Ul’yanova 1, Nizhni Novgorod, 603005 Russia
Lobachevsky Nizhni Novgorod State University, pr. Gagarina 23, Nizhni Novgorod, 603950 Russia
Kargin Research Institute of Chemistry and Technology of Polymers with Pilot Plant,
Vostochnaya promzona, Dzerzhinsk, Nizhni Novgorod oblast, 606000 Russia
Received March 7, 2014
Abstract—Micellar catalysis with various polyoxyethylated compounds was used to synthesize sodium allyl
sulfonate by the reaction of allyl chloride with an aqueous solution of sodium sulﬁ te. It was shown that methoxy
polyethylene glycol methacrylates and water soluble polymers based on these compounds are surfactants and
can be used to intensify the synthesis of sodium allyl sulfonate, which is of interest in the case of its subsequent
application to obtain copolymers with methoxy polyethylene glycol methacrylates.
Sodium allyl sulfonate (SAS) is used as a half-product
for obtaining medicinal preparations and a comonomer
for manufacture of various polymers: acrylic synthetic
ﬁ bers, polymeric corrosion inhibitors, dispersing agents,
etc. [1–3]. One of new SAS application ﬁ elds is to obtain
carboxysulfo-containing polymeric superplasticizers for
concrete mixes [4, 5]. In the last 10–15 years, polycar-
boxylate superplasticizers synthesized on the basis of
methoxy polyethylene glycol methacrylates (MPEG-
MAs) and (meth)acrylic acid have found wide use in the
building industry developed countries on having driven
out the conventional superplasticizers based on sulfated
naphthalenes . Russia is preparing to set up a large-
scale manufacture of superplasticizers for concrete mixes.
Introduction of sulfoacid salt units into polycarboxylate
superplasticizers makes it possible to additionally raise
their dispersing capacity [4, 5].
Sodium allyl sulfonate is conventionally produced by
the reaction of allyl bromide  or allyl chloride (AC)
with sodium sulﬁ te (SS):
Hal + Na
Na + NaHal, (1)
where Hal = Cl (AC), Br.
The reaction is performed under vigorous stirring of
a heterogeneous mixture of allyl halides, which are hardly
soluble in water, and an aqueous solution of CC. The
target product being formed is well soluble in water and
fully passes to the aqueous phase. As regards prospects
for application of SAS for manufacture of large-tonnage
polymers, use of more accessible and less expensive AC
have clearly pronounced advantages. However, AC is
strongly inferior to allyl bromide in activity and using
more severe process conditions and making longer the
synthesis duration are restricted by the easy occurrence
of side reactions of AC hydrolysis and polymerization.
In addition, when choosing the process conditions, it is
necessary to take into account the low boiling point of
the azeotrope formed by AC and water (43°C).