ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 3, pp. 360 !369. + Pleiades Publishing, Ltd., 2008.
Original Russian Text + E.A. Gurkovskaya, 2008, published in Zhurnal Prikladnoi Khimii, 2008, Vol. 81, No. 3, pp. 374 !383.
Thin-Layer Size-Exclusion Chromatography of Polymers
E. A. Gurkovskaya
Moscow State University of Technology and Management, Moscow, Russia
Received May 15, 2007
Abstract-Modern concepts of thin-layer chromatography of macromolecular compounds are reviewed,
including the features and potentialities of thin-layer size-exclusion chromatography.
The use of thin-layer chromatography (TLC) for
analysis of polymers was a sign of a big success of
this method. The first TLC studies of random poly-
mers were reported in 1968 [1, 2]. Since that the
primary research direction in the field of TLC of poly-
mers was associated with the use of this method for
characterization of the polydispersity of polymers
(compositional and molecular heterogeneity) and
identification of polymers of various classes [3, 5].
The use of TLC allowed separation of random copoly-
mers; identification of random, block, and alternating
copolymers; identification and separation of di- and
triblock copolymers; separation of block and graft
copolymers from homopolymers; identification and
separation of stereoregular poly(methyl methacrylates)
(PMMAs) and polystyrenes (PSs) of various micro-
tacticities; separation of geometric isomers of poly-
butadiene (PBD) and polyisoprene (PI); and iden-
tification of linear and branched PSs as well as PSs
with different terminal groups and their separation
from bi- and multifunctional PSs. In polymer separa-
tions, combined TLC methods are often used, e.g.,
polymer separation at the origin by selective desorp-
tion, followed by fractionation using adsorption or
precipitation TLC. Adsorption TLC (ATLC) was first
suggested for separation of copolymers [1, 3, 6, 7] and
employed for MWD analysis in homopolymers .
To fractionate polymers by the molecular weight,
Inagaki et al. [9, 10] proposed precipitation TLC
All the versions of TLC of polymers can be sub-
divided into two groups. The first group covers the
methods based on adsorption. The second group in-
cludes the methods based on phase distribution of
polymer solutions: precipitation and extraction TLC.
Extraction TLC (ETLC) of polymers is based on
selective dissolution of polymer solution at the origin.
It has been used for separation of isotactic and atactic
PMMA  and PS .
Thin-layer size-exclusion chromatography (TLSEC)
of polymers is based on the molecular-sieve effect. In
this technique, adsorption of polymers is suppressed,
and the pore space of the sorbent is presaturated with
a solvent either by virtue of capillary condensation in
exposing the plate to solvent vapor [3, 8] or by using
so-called preelution  (passing a solvent through
the chromatographic layer prior to applying a sample
to be analyzed). The process is schematically shown
in Fig. 1.
Fig. 1. Schematic of thin-layer size-exclusion chromatog-
raphy. (L) Plate length and (b) plate width; (b) plate angle;
) geometric head; and (U) mobile phase flow rate.
(1, 5) Development tanks, (2) start line, (3) sorbent layer,
(4) layer thickness control, and (6) glass support.