Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 3, pp. 423−426.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © E.I. Yarmukhamedova, Yu.I. Puzina, M.A. Gafarov, P.Yu. Puzin, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86, No. 3,
AND POLYMERIC MATERIALS
Increase in the Content of Maleic Anhydride Units
in a Copolymer with Methyl Methacrylate
in the Presence of 1,3,5-Trithiane
E. I. Yarmukhamedova
, Yu. I. Puzin
, M. A. Gafarov
, and P. Yu. Puzin
Institute of Organic Chemistry, Ufa Scientiﬁ c Center, Russian Academy of Sciences,
Ufa, Bashkortostan, Russia
Ufa State Petroleum Technical University, Ufa, Bashkortostan, Russia
Neftekhim Pilot Plant, Private Joint-Stock Company, Ufa, Bashkortostan, Russia
Received November 6, 2012
Abstract—The use of 1,3,5-trithiane as agent controlling copolymerization of maleic anhydride with methyl
methacrylate allows preparation of the copolymer with increased content of anhydride units because of the radical
complex mechanism of the process under these conditions.
Many maleic anhydride (MA) copolymers and
their modiﬁ cation products are used in production of
various polymeric coatings and of polymeric additives
in pretreatment and transport of crude oil. These
copolymers are also convenient starting substances
for preparing new copolymers that have found use as
biologically active substances, enzyme carriers, and
pore-forming, lubricating, and other materials [1, 2].
On the other hand, MA homopolymers are not used,
because their preparation is practically unfeasible.
However, it is possible to increase the content of MA
units in copolymers, e.g., by enhancing the MA activity
in copolymerization via complexation .
It is known that maleic anhydride can form
complexes with various compounds. Depending on
the nature of the second component, π electrons of the
multiple bond or carbonyl group of MA can participate
in the complexation [2, 3].
Organic sulfur compounds also actively participate
in formation of complex compounds. Studies of
polymerization in their presence showed that these
compounds can control kinetic parameters of the
polymerization, participating both in chain initiation [4,
5] and in chain propagation and termination ; they
can also affect the molecular-weight characteristics and
microstructure of the polymers [7, 8].
Thus study deals with radical copolymerization
of methyl methacrylate and maleic anhydride in the
presence of 1,3,5-trithiane, a sulfur compound capable
of transformations in the course of formation of redox
systems (RSs). As we found previously [8, 9], in the
course of radical polymerization of methyl methacrylate
1,3,5-trithiane (ТТ) reacts with both peroxy and azo
initiators, ensuring occurrence of the polymerization
by the radical complex mechanism and allowing
preparation of poly(methyl methacrylate) of decreased
Methyl methacrylate (MMA) and the initiator
[azobis(isobutyronitrile), AIBN] were puriﬁ ed by pub-
lished procedures . Commercial 1,3,5-trithiane (Al-
drich, no. Т8,840-4) was recrystallized from methanol,