ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 9, pp. 1490!1493. C Pleiades Publishing, Inc., 2006.
Original Russian Text C G.M. Pavlov, I.I. Zaitseva, A.S. Gubarev, I.I. Gavrilova, E.F. Panarin, 2006, published in Zhurnal Prikladnoi Khimii, 2006,
Vol. 79, No. 9, pp. 1506!1509.
AND POLYMERIC MATERIALS
Diffusion-Viscometric Analysis and Conformational
Characteristics of Sodium Polystyrenesulfonate Molecules
G. M. Pavlov, I. I. Zaitseva, A. S. Gubarev, I. I. Gavrilova, and E. F. Panarin
Fock Research Institute of Physics, St. Petersburg State University, St. Petersburg, Russia
Institute of Macromolecular Compounds, Russian Academy of Science, St. Petersburg, Russia
Received June 5, 2006
Abstract-Samples of sodium polystyrenesulfonate of molecular weights varying in a 20-fold range were
synthesized. The hydrodynamic behavior of the samples was studied in a 0.2 M NaCl solution in which
the initial polyelectrolyte effects are suppressed. Relationships between the molecular weight and the transla-
tional friction coefficient and intrinsic viscosity were obtained. The theory describing the hydrodynamic
behavior of wormlike chains with taking into account both the percolation effects and the excluded-volume
effects was applied to estimation of the length of the statistical segment and the cross section of the sodium
polystyrenesulfonate molecules in 0.2 M NaCl solution.
Ionic macromolecules, polyelectrolytes, play an
important role in animate nature and in various in-
dustrial processes [13 4]. Studies of polyelectolytes are
of great interest, since their macromolecules are re-
presented by chains with variable equilibrium rigidity
governed by the linear charge density, ionic strength
of solution, and the structure of the monomeric unit.
Recently the interest in studies of charged macro-
molecules increased again; new theoretical approaches
were developed that describe the behavior of this class
of polymers, more complex than neutral polymers
[13 6]. At the same time, systematic quantitative
studies of the molecular characteristics and properties
of polyelectrolytes are much less in number than those
in the databank describing the behavior of neutral
In this study we extended the scope of many-year
studies of water-soluble polymers and examined the
hydrodynamic and molecular characteristics of sodium
Polymerization of styrene-4-sulornate was carried
out in an H
O : DMF = 1 : 1 solution at 60oC for 24 h
with various concentrations of AIBN in sealed am-
pules. The resulting polymer was precipitated into
acetone and dried in a vacuum to constant weight.
The hydrodynamic characteristics were studied in
0.2 M NaCl solution. The translational diffusion was
studied in a Tsvetkov’s diffusometer  by the clas-
sical method of formation of solution3solvent bound-
ary, which was fixed at regular intervals with a polari-
zation interferometer [12, 13]. The diffusion inter-
ferograms were processed by the maximal ordinate
and area method . The diffusion coefficient D =
/Dt)/2 was estimated from the slope of the experi-
mental dependences of the variance s
of the diffu-
sion boundary on the time of experiment t (Fig. 1).
Fig. 1. Dependence of the variance of the diffusion bound-
, on the diffusion time t, min, for sodium poly-
styrene sulfonate samples in 0.2 M NaCl solution at 25oC.
Figures at straight lines correspond to sample nos. in the
table; the same for Figs. 2 and 3.