1070-4272/03/7611-1870$25.00C2003 MAIK [Nauka/Interperiodica]
Russian Journal of Applied Chemistry, Vol. 76, No. 11, 2003, pp. 1870!1872. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 11,
2003, pp. 1921!1923.
Original Russian Text Copyright + 2003 by Lesnyak, Gaponik, Mardykin, Kaputskii.
Sulfonated Petroleum Polymeric Resins
as Plasticizers for Cement Mortars
V. P. Lesnyak, L. V. Gaponik, V. P. Mardykin, and F. N. Kaputskii
Research Institute of Physicochemical Problems, Belarussian State University, Minsk, Belarus
Received July 1, 2003
Abstract-Sulfonation of petroleum polymeric resins based on the C
fraction with various suilfonatic agents
was studied, and procedure was developed for preparing sulfonated resins. The possibility of using sulfo resins
as effective plasticizers for concrete was examined.
Sulfonation of hydrocarbon polymers is one of
effective modification procedures extending the appli-
cation field of these materials. Introduction of sulfo
groups makes polymers hydrophilic, which allows
their use as water-soluble components of various
Efficient sulfonation procedures were developed for
polymers and copolymers of ethylene and styrene [13
3]. In the case of petroleum polymeric resins (PPSs),
which are multicomponent systems involving about
ten kinds of monomeric units, sulfonation procedures
virtually have not been studied. Petroleum polymeric
resins are today one of the most promising and cheap-
est synthetic substitutes of vegetable oils and rosins.
These products are prepared from by-products of oil
pyrolysis and are widely used in production of syn-
thetic drying oils, oil3resin lacquers, and components
of various paint-and-varnish, adhesive, rubber, and
other formulations. However, PPR-based products are,
as a rule, soluble only in aromatic hydrocarbons and
alkyl halides and insoluble in water, which restricts
their applications. Modification of PPRs by sulfona-
tion will give environmentally friendlier water-soluble
film-forming agents and plasticizers.
Our studies resulted in development of a waste-free
process for production of PPRs and petroleum poly-
merizate (PP), an analog of petroleum polymeric dry-
ing oil, by cationic polymerization of the C
There products are intended for use as film-forming
agents in paint-and-varnish production .
The goal of this work was to study sulfonation of
PPRs and prepare from them a plasticizing additive
to cement mortars.
Published data and preliminary experiments on
sulfonation of styrene oligomer (molecular weight
100033000) revealed the regular trends and optimal
conditions of the process and allows us to find the
best sulfonating agents (SAs) for PPRs of molecular
weights 500 and 800 .
Sulfonation was performed under mild conditions
(at 0335oC) in a halogenated hydrocarbon solvent.
As sulfonating agents we used 10334% oleum, liquid
, acetyl sulfate, chlorosulfonic and sulfuric acids,
and 2 : 1 and 1 : 1 SO
3dioxane complexes. The latter
agents appeared to be the most effective. The complex
.dioxane was prepared at 035oC in a reactor
equipped with a power-driven stirrer, a dropping fun-
nel, and a thermometer, by slowly adding 1,4-dioxane
to a solution of SO
in chloroform. To the resulting
complex of SO
with dioxane or to another SA, a
solution of PPR or PP in chloroform was added over a
period of 233 h with vigorous stirring. After adding
the whole amount of PPR (or PP), the mixture was
stirred for an additional 1 h and then diluted with
water and neutralized with sodium carbonate. The
aqueous and organic layers were separated in a sep-
aratory funnel. The aqueous layer was filtered and di-
alyzed for 24 h. The purified solution was evaporated
on a rotary evaporator to obtain sulfo-PPR (SPPR).
The influence of the reactant ratio on the SPPR
yield and content of HSO
groups is illustrated by the
table. Sulfonation of PPR with sulfuric acid yields a
product that is virtually insoluble in water, probably
owing to formation of sulfone derivatives. With acetyl
sulfate, oleum, or liquid SO
used as sulfonating
agents, partially water-soluble products were obtained,
but their yield and content of sulfo groups were lower
as compared to the resins sulfonated with SO
ane complexes and chlorosulfonic acid.
The reactant ratio noticeably affects the content of