Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 5, pp. 873−876.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © E.I. Yarmukhamedova, Yu.I. Puzina, I.A. Ionova, Yu.B. Monakov, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84,
No. 5, pp. 844−847.
AND POLYMERIC MATERIALS
Preparation of Low-Polydispersity Poly(Methyl Methacrylate)
in the Presence of 1,3,5-Trithiane
E. I. Yarmukhamedova
, Yu. I. Puzin
, I. A. Ionova
, and Yu. B. Monakov
Institute of Organic Chemistry, Ufa Scientiﬁ c Center, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
Ufa State Petroleum Technical University, Ufa, Bashkortostan, Russia
Received July 19, 2010
Abstract—The mechanism of methyl methacrylate polymerization in the presence of 1,3,5-trithiane was studied
The polydispersity is an important characteristic
of macromolecular compounds . It often exerts
a decisive effect on the service properties of polymers:
Simultaneous presence in a sample of macromolecules
that appreciably differ in the size, weight, and pendant
chains, but are practically indiscernible in chemical
properties gives rise to heterogeneities with respect to
virtually all physicomechanical properties (elasticity,
brittleness, ﬂ owability, etc.).
Furthermore, scatter in the molecular weight
of macromolecules depends on the polymerization
conditions: If the process occurs by the radical
mechanism, the polydispersity is usually about 2.0, and
if it occurs by the ionic (ionic-coordination) mechanism,
it is about 1.0 [1, 2].
Recently there had been a great deal of interest in
polymerization processes occurring by the complex-
radical mechanism , in the living chain mode .
Various compounds are used as additives making
the process to occur in the complex-radical, or living
polymerization, mode. For example, addition of Cu(II)
complex salts allows not only acceleration of the
polymerization by a factor of 5, but also preparation
of the polymer with a polydispersity of 1.05–1.3 .
With palladium(II) acetylacetonate, the polydispersity
of poly(methyl methacrylate) (PMMA) was 1.4–1.6 .
In contrast to these compounds, metallocenes such as
ferrocene , titanocene, and zirconocene , as well
as porphyrin compounds , appreciably accelerate the
polymerization, but do not noticeably affect the polymer
Heteroatomic organic compounds are also known as
additives actively affecting both the rate and the degree
of polymerization. For example, a number of organic
amines accelerates the polymerization and affects the
microstructure of the polymer [8, 9]. However, in this
case the polydispersity of the polymers is 1.9–2.0.
Experiments with geminal bissulﬁ des showed 
that the polymerization in their presence is accelerated
under deﬁ nite conditions, but no information is given in
 on the polymer polydispersity.
In this study we examined how a cyclic geminal
trissulﬁ de, 1,3,5-trithiane (TT), affects the polymerization
of methyl methacrylate and the polydispersity of the
Methyl methacrylate (MMA) and the initiator
[benzoyl peroxide (BP), azobis(isobutyronitrile)
(AIBN)] were puriﬁ ed by published procedures .