Russian Journal of Applied Chemistry, 2013, Vol. 86, No. 10, pp. 1549−1562.
Pleiades Publishing, Ltd., 2013.
Original Russian Text © P.B. Pirozhnikov, I.V. Korolev, N.G. Kuzina, L.N. Mashlyakovskii, 2013, published in Zhurnal Prikladnoi Khimii, 2013, Vol. 86,
No. 10, pp. 1595−1609.
AND POLYMERIC MATERIALS
Hyperbranched Polymers and Their Use in the Technology
of Paint-and-Varnish Materials and Coatings (A Review)
P. B. Pirozhnikov, I. V. Korolev, N. G. Kuzina, and L. N. Mashlyakovskii
St. Petersburg State Institute of Technology (Technical University), St. Petersburg, Russia;
Received June 26, 2013
Abstract—The main approaches to “assembling” of dendritic polymers of various architectures are considered.
Types of dendritic polymers are generalized, and the main criteria for evaluating their topology, physicochemical
properties, and application ﬁ elds are outlined. The possibility of using commercially produced hyperbranched
polymers for modiﬁ cation of the operation properties of polymeric materials is demonstrated. Particular attention
is paid to the use of hyperbranched polymers as precursors for preparing modiﬁ ers of the surface properties of
The history of the development of highly branched
polymers (HiBPs) covers more than a century. The ﬁ rst
representatives of such polymers were prepared as early
as the end of XIX–beginning of XX century [1, 2]. How-
ever, unique properties of HiBPs, distinguishing them
both from common linear polymers and from network
macromolecular structures , have been discovered only
in the past decade. Such properties make these polymers
very promising for use in such important ﬁ elds as mi-
croelectronics [4, 5], medicine [6, 7], optics [8, 9], etc.
Unfortunately, despite acute need in practical imple-
mentation of the modern achievements in the ﬁ eld of
polymers, including primarily such revolutionary poly-
mers as HiBPs, studies on practical use of HiBPs in
Russia are few.
A source of unique properties of HiBPs is their unusual
core–shell structure with very high local concentration
of terminal groups in the peripheral layer (shell) of mac-
romolecules and high local concentration of branching
points in the core . Therefore, on reaching certain
degree of branching, the hydrodynamic diameter of the
polymer increases only slightly with an increase in the
molecular weight (Table 1). Starting from a certain mo-
lecular weight (М
), the hydrodynamic volume of
HiBPs becomes considerably smaller than that of linear
macromolecules of the same molecular weight . Such
more compact packing of HiBP macromolecules and
large amount of free terminal groups on their periphery
open prospects for using such polymers in the technol-
ogy of paint and varnish materials (PVMs) and coatings
not only as ﬁ lm-forming agents of new generation, but
also as modiﬁ ers for considerably enhancing the adhe-
sion, reducing the brittleness and internal stresses, and
improving the optical, protective, and other operation
characteristics of the coatings.
PROCEDURES FOR PREPARING DENDRITIC
In 1987, Kim and Webster synthesized an HiBP of
dendritic structure from 3,5-dibromophenylboronic acid
[11, 12]. They introduced the term dendrimer originating
from a combination of two Greek words: dendri (resem-
bling a tree) and meros (part) . This term was applied
to HiBPs owing to their unusual structure  (Fig. 1).
The tree-like HiBPs subsequently got a common name,
dendritic polymers (DPs). Their distinctive feature is
strongly branched dendritic structure with a large amount
of terminal groups.
There are two synthetic approaches to DP preparation,