ISSN 1811-2382, Polymer Science, Ser. C, 2007, Vol. 49, No. 4, pp. 332–354. © Pleiades Publishing, Ltd., 2007.

Original Russian Text © G.V. Korolev, M.L. Bubnova, 2007, published in Vysokomolekulyarnye Soedineniya, Ser. C, 2007, Vol. 49, No. 7, pp. 1357–1388.

Synthesis, Properties, and Practical Application

of Hyperbranched Polymers1
G. V. Korolev† and M. L. Bubnova
Institute of Problems of Chemical Physics, Russian Academy of Sciences,
pr. Akademika Semenova 1, Chernogolovka, Moscow oblast, 142432 Russia
e-mail: bml@icp.ac.ru

Abstract—The methods of synthesis of hyperbranched polymers are considered and systematized with main
attention focused on such modern and promising procedures of crosslinking free-radical polymerization as liv-
ing chain and intense chain transfer regimes. The synthetic approach to hyperbranched polymers via free-rad-
ical oxidative polymerization is the first to be put forth. The main problems concerning these polymers are for-
mulated, and the recent advances in this field are generalized and elucidated.
DOI: 10.1134/S1811238207040030

INTRODUCTION:
DEFINITIONS, HISTORICAL REVIEW,
AND DEVELOPMENT
Polyaddition (polymerization) reactions of any
monomers may be divided into two groups, namely, lin-
ear and crosslinking, depending on the number of
bonds that can be formed by a given monomer mole-
cule (i.e., depending on its functionality). If functional-
ity Φ is two, polymerization leads to the formation of
threadlike macromolecules, i.e., linear chains, while at
Φ > 2, branched chains appear whose degree of branch-
ing continuously increases in the course of propagation
of macromolecules (crosslinking polymerization). In
this case, at the moment of the complete consumption
of the monomer, the polymerization product becomes
either a hyperbranched polymer (HBP) or acquires of a
topological structure of a three-dimensional network
type (all monomer units are linked via the continuous
network of bonds).
In the 1950s, Flory formulated conditions favorable
for the synthesis of HBPs via the step-growth polyaddi-
tion (polycondensation) reactions and unfavorable for
the formation of networks (e.g., [1]). In the simplest
case, an AB2 monomer, where A and B are functional
groups that can be involved in the addition reaction A +
B AB, is required. Given this, the formation of
HBPs may be schematically represented as
† Deceased.
1 This work was supported by the Russian Foundation for Basic
Research, project nos. 06-03-07000 and 06-03-32543a.
B
B
A
A A B
B + nAB2 BA
B
B BA
B
B
The double encircled molecule ÄB2 will serve as a cen-
ter of symmetry from which branches emanate and the
number of branches doubling after each event of addi-
tion of subsequent monomer molecules AB2. As is
seen, the probability of the intramolecular addition A +
B (the so-called cyclization) is very small and progres-
sively decreases with the propagation of a macromole-
cule; at the first stage, there are five B groups per func-
tional group A (after the first cascade of addition—the
formation of the first generation), then there are 11 B
groups (after the formation of the second generation),
and, eventually, 23 groups (after the third generation).
Usually, three to six generations have time to form dur-
ing the synthesis of HBPs via the polycondensation of
AB2. Such a topological structure that practically lacks
cycles is referred to as HBP [1].
Later, HBPs remained outside the focus of research-
ers for a long time (for more than two decades) until a
new family of HBPs, i.e., dendrimers, appeared. The
difference between these new HBPs and the irregular
(random) structures of conventional HBPs involves a
strict structural regularity achieved via multistep syn-

332
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
thesis; formation of each subsequent generation neces-
sitates a new synthetic stage. It turned out that dendrim-
ers exhibit unique properties, as a result of which these
polymers show promise for extremely efficient practi-
cal applications. Numerous publications and reviews
on this subject have been published (i.e., [2]). However,
the practical use of dendrimers was limited by the fact
that their synthesis procedure is laborious and, accord-
ingly, their price is high. This circumstance stimulated
the outbreak of interest in conventional HBPs whose
behavior had been poorly studied. Shortly after that, it
was demonstrated that conventional statistical HBPs
synthesized by means of substantially simpler methods,
like dendrimers, possess the same unique characteris-
tics.
This discovery was of such paramount significance
that HBPs began to be used to a greater advantage in the
most important fields (polymer materials science, elec-
tronics and microelectronics, optics, biology, medicine,
and ecology) within an extremely short period of time.
An important field of polymer science, i.e., crosslink-
ing polymerization, whose long-term intense and suc-
cessful research was nearing its end, gave impetus to
the development of studies on the basis of new unusual
facts related to studies. The dynamics of the growth of
the number of publications in this filed that reflects the
intensity of its development is of a revolutionary char-
acter; at the beginning of the 1990s, single publications
appeared; at 2000, this number was nearly 200, while in
2003–2005, more than 250 papers were published
annually. In 2006, this rate was maintained, judging by
the rate of publications in the first half-year. Note that
over the past five years, the number of reviews devoted
to HBPs was also recorded, and amounted to no less
than two reviews annually.
This paper is in fact the first Russian review that
fully covers the field of HBPs, because the review by
Bochkarev and Katkova (Usp. Khim., 1995) [3] consid-
ered only a limited number of issues (mostly the syn-
thesis of HBPs from organometallic monomers), while
the review by Semchikov in Sorosovskii Obrazova-
tel’nyi Zhurnal, 1998) [4] does not reflect the rapidly
developing area of HBPs.
It should be noted that the idea of HBPs is a debated
topic. The matter is that the strict definition of HBPs is
purely topological and is based on Flory’s studies dat-
ing back to the middle of the last century. According to
Flory, an HBP is a branching symmetric macromole-
cule with the number of branches that grow progres-
sively as they move away from the center of symmetry
and are almost completely lacking in cyclized moieties.
However, recent investigations have shown that par-
tially cyclized branched macromolecules also demon-
strate unique properties inherent to classical HBPs. As
a consequence, a purely topological definition was
changed for a more pragmatic notion that relies on
whether a progressively branching macromolecule pos-
sesses or lacks a set of unique distinguishing (distin-
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
333
guishing from linear macromolecules) features, such as
high solubility and thermodynamic compatibility, low
viscosity of solutions, a weakening of the dependence
of the hydrodynamic volume of macromolecules on
their molecular mass with an increase in this parameter,
and, finally, the ability of HBP macromolecules to
serve as nanocontainers for guest molecules during
their interphase transfer. The latter properties are
related to the specific structure of HBP macromole-
cules of the core–shell type, which allows for the strong
sorption of guest molecules in a looser core and, thus,
the formation of solutions of sorbate molecules in
media in which they are insoluble and HBP is soluble.
Nearly all publications are currently based on the
above-mentioned pragmatic definition of HBPs.
This approach is associated with the revolutionary
break in the practical application of the polymers in
question, where the major criteria are, firstly, the pres-
ence of unique properties of HBPs and, secondly, ease
of synthesis and the low price of these polymers, along
with their processibility and the feasibility of large-
scale manufacture. In this case, a certain number of
cycles in HBP macromolecules, compared to the ideal
Flory structure, plays an insignificant role until it
exceeds a certain criterial value, after which the specific
core–shell structure can no longer be formed and a
microgel is formed instead of the HBP. This microgel
differs from the HBP in its associative ability in solu-
tions; namely, the microgel is less stable in highly con-
centrated solutions (as opposed to the HBP).
It should be emphasized that none of the subjects of
this review belongs to the class of micro- and macro-
gels since they exhibit a well-defined combination of
unique characteristics typical of HBPs.
HBPs may be rather fully described in terms of the
following two parameters: chemical and topological
structures of macromolecules. The chemical structure
is the totality of atomic groups in HBP macromole-
cules. The topological structure is determined by the
number of chains (arms) emanating from the center of
symmetry, the number of cascades of branchings (gen-
erations), the number of branch points (junctions) in
each cascade, and the length of chain fragments
between neighboring junctions (interjunction chains).
Modern analytical procedures (chemical analysis and
1H and 13C NMR spectroscopy) make it possible to
determine rather reliably the above-mentioned charac-
teristics parameters of HBP, namely, chemical and
topological structures controlling the main macro-
scopic properties of hyperbranched macromolecules.
However, these properties are also determined by
another parameter, i.e., a network of labile (physical)
intermolecular bonds inside HBP macromolecules.
Along with barriers to the rotation of atomic groups,
this network specifies the conformational states of the
elements of the topological structure and, accordingly,
the distribution of the molecular packing density in the
volume of macromolecules. Computer simulation of
334 KOROLEV, BUBNOVA
macromolecules by means of molecular mechanics and
molecular dynamics methods provides the most reli-
able information of this kind. However, the operating
speed of modern computers confines the potential of
such a simulation; unattainable calculation times are
needed for multiatomic macromolecules of HBPs even
if the highest speed most computers of the latest gener-
ations are used. If one does not go beyond the separate
structural fragments of HBP macromolecules, informa-
tion concerning any local features of the molecular
packing may be derived and the reliability of this infor-
mation may turn questionable because of the neglected
effect of neighboring fragments. It is expected that
rapid progress in computer engineering will make it
possible to solve this problem in the near future.
STATE OF THE ART AND MOST URGENT
PROBLEMS IN THE AREA OF HBPS
Formulation of Main Issues
One of the most significant issues is the synthesis of
HBPs via economically reasonable methods that are
acceptable in terms of engineering. An analysis of a
huge (more than 600 sources) body of publications
devoted to HBPs in the past decade leads us to conclude
that this synthetic problem is regarded currently as the
most pressing in world science. In terms of the modern
macromolecular design, this issue may be most unam-
biguously formulated as follows: the development of
methods for the chemical design of HBP macromole-
cules with the desired topological architecture, desired
set of functional groups, and desired length of flexibil-
ity of interjunction chains in order to provide a wide
assortment of HBP characteristics necessary for solv-
ing specific practical problems.
Problems related to the chemical design of macro-
molecules are largely solved via the following synthetic
procedures:
(1) Traditional step polyaddition (polycondensa-
tion) reactions that include reagents in accordance with
Flory’s schemes [1], among which the most reliable
scheme involves monomer AB2. More than one hun-
dred years ago, Berzelius used this scheme for the syn-
thesis of the first HBP via the esterification reaction and
the Perstorp Specialty Chemicals AB (Sweden) with a
division Perstorp Polyols Inc. (USA) primarily
employs 2,2-dimethylolpropionic acid as AB2 for the
manufacture of HBPs under the trademark Boltorn. A
substantially new approach involves the use of small
additives of higher functionality comonomers ABn (or
AnB), where n
2, as seeds to afford the multiarm
topological structure of macromolecules (rather than
the three-arm structure typical of AB2 in the absence of
additives). A new and important direction in this tradi-
tional field includes the search for two-stage processes
characterized by strict kinetic differentiation of both
stages. The first stage leads to the quantitative transfor-
mation of the starting reagents into monomer AB2,
which undergoes polycondensation at the second stage
to yield HBPs. Numerous variants of such two-stage
processes were advantageously implemented by Gao
et al. [5]; as a result, the assortment of hyperbranched
polymers has been extremely widened owing to the use
of a large number of starting compounds accessible in
terms of economics and engineering.
(2) Crosslinking radical (co)polymerization carried
out in the living chain mode. This phenomenon, which
was discovered rather recently [6], is widely used for
the synthesis of HBPs, especially in the case of HBPs
with complex topological structures (the so-called
nanostructured HBPs whose macromolecules are
shaped as one- or two-layer cylinders, spheres strung
on a linear chain, or dumbbells).
(3) Conventional crosslinking radical polymeriza-
tion conducted under conditions providing formation of
supershort chains, since the formation of long chains
leads to an increase in the probability of the cyclization
of the branchings being formed to such an extent that a
microgel develops instead of the HBP. Along with
tricks used to shorten chains via the addition of conven-
tional chain-transfer agents or the use of a rather new
chain-transfer catalysis phenomenon [7], other
approaches were elaborated, for example, the use of
superhigh rates of initiation [8] and the discovery of
intrachain reactions of propagation radical that termi-
nate the growth of substantial chains [9].
Radical polymerization differs appreciably from the
step polyaddition (polycondensation) reactions in the
mechanism of macromolecule growth; in the case of
polycondensation, the addition of new monomer units
to macromolecules requires that the activation barrier
E = 63–84 kJ/mol be overcome each time. This barrier
is inherent to esterification, migration polymerization,
and other polycondensation processes. Therefore, the
slow growth of macromolecules takes place and the
time of this process is commensurable with the time
polycondensation itself. In the case of radical polymer-
ization, a high activation barrier E = 50–126 kJ/mol is
overcome only at the very beginning of the growth of
macromolecules during formation of initiating radical
and further chain growth proceeds with low values of
E < 42 kJ/mol, that is, extremely rapidly (instanta-
neously relative to the duration of polymerization). The
well-known Flory–Stockmayer theory describing for-
mation of branched and network structures (and gela-
tion) was developed as applied to polycondensation and
appears to be inapplicable to radical polymerization.
The use of radical polymerization for the synthesis of
HBPs needs the elaboration of the corresponding the-
ory of gelation for prediction of limiting yields of the
target product and formulation of synthesis conditions
ensuring the highest yield. This situation generated the
need to advance a new theory of gelation specially elab-
orated for crosslinking radical polymerization pro-
cesses. This issue is covered in a number of theoretical
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
studies, among which a publication is the most repre-
sentative [10].
After the commercial production of HBPs was
launched (for the time being only in Europe), another
problem directly related to the chemical design
evolved; namely, the search for simple and well-con-
trollable reactions of the addition to functional groups
of commercial standardized and well-characterized
HBPs aimed at their modification as applied to specific
practical tasks. For example, the HBPs of the Boltron
family [11] (Perstorp Specialty Chemicals AB, Swe-
den) contain a certain number of hydroxyl groups (16,
32, 64, and 128, respectively) depending on the trade-
mark (H20, H30, H40, and H50). Evidently, the pres-
ence of a large amount of polar groups ensures good
thermodynamic affinity (and hence, solubility and com-
patibility) only in polar media. The esterification of
fatty acids (or epoxidized fatty acids) of the predeter-
mined amount of hydroxyl groups allows one to control
the level of thermodynamic affinity over a wide range,
including the affinity for weakly polar media upon full
esterification of all hydroxyl groups. If esterification is
carried out with the use of epoxidized fatty acids, epoxy
groups impart an additional feature:corresponding
reactivity. Thus, a rather narrow range of basic industri-
ally produced HBPs may be easily extended in the
desired direction if simple and well-controlled polyad-
dition reactions are developed. This issue, as evidenced
by the published data, has received much attention.
The successful solution of the chemical design for
the polymers under consideration is inevitably associ-
ated with the simultaneous solution of the problem con-
cerning the reliable identification of the topological
structure and molecular parameters of HBP macromol-
ecules (including the hydrodynamic volume and
shape). This problem may be solved via both the
employment of conventional methods (any variants of
electron microscopy, for example, transmission and
dark-field, high-resolution 1H and 13C NMR spectros-
copy, mass spectrometry, and IR spectroscopy) and the
elaboration of special methodologies designed spe-
cially for HBPs. This primarily concerns the GPC
methods of molecular mass distribution measurements
that are based on the proportionality between molecular
masses and hydrodynamic volumes of macromole-
cules. However, it turns out that because of the specific
molecular packing of HBP macromolecules, the hydro-
dynamic volume initially grows more slowly than
molecular mass and then remains practically invariable
and insensitive to further increases in molecular mass.
Therefore, the classical GPC procedure with the use of
a single detector (as a rule, refractometric) is inapplica-
ble to molecular mass distribution measurements of
hyperbranched polymers. For this case, a special mul-
tidetector variant of GPC was developed (with the use
of additional IR-spectroscopic detector and, what is
especially important, with the use of the laser detector
for small-angle or multiangle scattering measure-
ments). Furthermore, the latest variant of mass spec-
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
335
trometry is used in this field, namely, matrix-assisted
laser desorption/ionization time-of-flight mass spec-
trometry (MALDI-TOF).
It should be emphasized that high-resolution NMR
spectroscopy provides a rather differentiated system of
chemical shifts for chemically slightly differing frag-
ments of HBP macromolecules, such as, for example,
branched and unbranched units only if the latest instru-
ments operating at frequencies of no less than 500 MHz
for 1H nuclei and of no less than 300 MHz for 13C
nuclei.
Another issue (the interplay between the chemical
and topological structures of HBP macromolecules and
macroscopic properties) is of utmost importance and, at
the same time, the least studied. It should be noted that
a similar problem for less complex macromolecules,
for example, linear (co)polymers has been solved
already for several decades. However, no reliable sys-
tem for predicting macroscopic properties has been cre-
ated until now. A great deal of the experimental data is
mostly analyzed by the method of increments that
allows one to perform only the interpolation prognosis
and is inapplicable to the extrapolation prognosis. As
regards hyperbranched polymers, this issue has been
poorly studied. Moreover, in the case of these poly-
mers, the topological factor is more significant and
hardly-interpretable than that in the case of other poly-
mers, where the chemical structure plays the key role.
Within the framework of the said issue, a special posi-
tion is occupied by the study of one of the most impor-
tant macroscopic characteristics of hyperbranched
polymers, i.e., the sorption and desorption ability of
HBP macromolecules relative to guest molecules,
depending on the nature of the medium in which the
sorption (or desorption) process takes place. Unfortu-
nately, very little information concerning this issue is
available in the literature (possibly because this infor-
mation is of great significance for practice and, there-
fore, is stored as confidential). The sorption (desorp-
tion) of hyperbranched polymers is a nontrivial process
since a sorbates is located in the inside HBP macromol-
ecules (in the core), while the kinetics of sorption (des-
orption) is controlled by the shell composed of func-
tional groups. The diffusion permeability of the shell
depends on the nature of intermolecular interactions
involving medium molecules in a complicated manner.
Gaining insight into the sorption–desorption process is
of extreme importance since this phenomenon forms
the basis of a unique feature of HBPs to serve as nano-
capsules for insoluble sorbates and nanosized particles
in phase-transfer processes, transport of drugs in
humans, and for the uniform distribution of insoluble
sorbates and nanoparticles in dispersion media.
Finally, the use of hyperbranched polymer in poly-
mer materials science (largely as modifying additives)
has demonstrated that in order to achieve high effi-
ciency in HBPs, it is necessary to solve the basic scien-
tific issue concerning the effect of HBP macromole-
336 KOROLEV, BUBNOVA
cules on the formation and properties of polymer matri-
ces of various types ranging from glassy (polyester,
polyepoxide, and polymethacrylate) to semicrystalline
(polyolefin, polycarbonate, and polyamide). An analy-
sis of the published data shows that the solution of this
problem is at the very beginning since a certain amount
of the experimental results has been accumulated but
systematic information necessary for generalization is
absent.
In what follows, we will consider the most impor-
tant studies concerning the main issues discussed
above.
The Contribution of Russian Researchers
to Solution of Actual Problems of HBPs
The most successful and significant progress has
been achieved by Russian researchers in the field of
synthesis of hyperbranched polymers (the chemical
design issue).
Thus, the school of academician Razuvaev (Nizhni
Novgorod) managed to create a new scientific direction
that made it possible to prepare one of the first HBPs,
i.e., perfluorinated poly(phenylenegermane)
[(C6H5)2Ge(C6H4)]n, via the one-step synthesis [12–
15]. Later on, this HBP was hybridized with linear
(co)polymers [16, 17]. As a result, the methods of the
synthesis of the HBPs of a complex molecular architec-
ture—nanostructured macromolecules with original
topologies—have been elaborated. Furthermore, on the
basis of HBPs of this kind, rare-earth metal complexes
(guest–host systems, where the guest complexon mole-
cule is situated in the core of the HBP host macromol-
ecule) have been synthesized. This original and unique
direction is of global importance [16–21].
Another synthetic strategy developed by Muzafarov
et al. is the chemical design of organosilicon hyper-
branched polymers with different degrees of order of
the topological structure ranging from extremely regu-
lar (dendrimers) to random disordered typical of HBPs
[22–28].
The most significant achievement of this direction is
the development of the one-step synthesis of HBPs via
the polycondensation of methyldiallylsilane
H Si , which functions here as a monomer of the
CH3
AB2 type. The synthesis of the HBP in the presence of
a platinum catalyst proceeds quantitatively within 24 h
at room temperature [25, 28].
New highly thermostable HBPs—poly(ester imi-
des) and copoly(ester imides)—have been prepared by
Kuznetsov et al. [29–32]. The synthesis was performed
by means of a new original method, i.e., high-tempera-
ture catalytic polycondensation in the melts of organic
acids.
As applied to medicine and biology, nanostructured,
hyperbranched macromolecules have been synthesized
via the hybridization of preformed dendrimers based on
aspartic (or glutamic) acid and linear highly reactive
polymer chains (poly(acryloyl chloride)) [33, 34].
The chemical design issue covers a set of theoretical
studies [10, 35–39] directed at the prediction of limit-
ing yields of HBPs and the formulation of the optimal
conditions for their synthesis. This set was completed
by the elaboration of a new theory of gelation intended
for crosslinking radical polymerization. The well-
known gelation theory advanced by Flory–Stockmayer
for step-growth polymerization (polycondensation)
appears to be inapplicable in this case.
The above-mentioned synthetic approaches are
being developed well and occupy a certain position in
world studies in the field of hyperbranched polymers.
However, this position is too low for a country such as
Russia, where organic and polymer chemistries have
conventionally been at a high level. This situation
becomes especially noticeable against the background
of an extremely intense stream of investigations from
abroad. Along with objective causes that require no
comment, there is another subjective reason for this
state of the domestic synthetic direction in the field of
interest. This is a certain backwardness of notions con-
cerning the idea of HBPs (see the above section, Intro-
duction). Until now, the greater part of leading Russian
researchers adhere to the purely topological (ideal) def-
inition of HBPs based on Flory’s work published half a
century ago. Naturally, this narrows down the range of
possible objects of research. One of the goals of this
review is to overcome this backwardness via the analy-
sis of a vast data array published by researchers from
abroad.
In addition to synthetic directions, there are many
studies dealing with other problems of HBs discussed
in the section titled “Formulation of Main Issues.” Indi-
vidual properties of HBPs or the feasibility of the prac-
tical use of HBPs of this kind for the manufacture of
articles and materials or particular theoretical issues are
primarily discussed [40–44].
CLASSIFICATION OF REACTIONS
FOR THE SYNTHESIS OF HYPERBRANCHED
POLYMERS
Difficulties encountered in the synthesis of HBPs
with desired characteristics (molecular mass, degree of
branching, and shape of macromolecules) are of differ-
ent characters depending on the type of the selected
synthetic reaction. An examination of these difficulties
and their classification leads to the following, and
apparently the most rational, classification of reactions
suitable for the synthesis of HBPs that have found use
in this field.
(1) Crosslinking polymerization occurring via the
step-growth polyaddition of the polycondensation type
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
(esterification, epoxy addition, urethane formation, and
addition of amine to multiple bonds).
(2) Crosslinking radical polymerization (CRP)
obeying the initiated chain polyaddition mechanism.
(3) Crosslinking radical polymerization proceeding
in the living chain mode. This is a peculiar case of CRP
since the growth of polymer chains follows the same
radical polyaddition chain mechanism as in the com-
mon CRP:
. kp . starting reagents and their concentration ratio) and is
Ri (M)n M + M(=) Ri (M)n + 1 M ,
where Ri is the initiator radical, M(=) is the multiple
bond in the starting monomer molecule, M are mono-
. case of radical-chain polyaddition; herein, a new gela-
mer units in a polymer chain, and M is the end unit car-
rying the free valence. However, this variant apprecia-
bly differs from the common CRP in that the chain
polyaddition mechanism degenerates to the step-
growth mechanism since because of the reversible inhi-
bition event,
. kx
Ri (M)n + 1 M + X kd
Ri (M)n + 1MX.
Provided the occurrence of the living chain mode, each
new polyaddition event (1) is inevitably preceded by
the event of the homolytic decomposition of
Ri (M)n + 1MX (reinitiation). In this case, reinitiation
proceeds with a sufficiently high activation energy, Ed =
105–126 kJ/mol, which is close to the activation energy
of the initiation, Ei = 117–126 kJ/mol, with typical ini-
tiators, such as organic peroxides and azodinitriles. In
other words, in contrast to the conventional CRP, where
after single initiation event, a polymer chain propagates
for a rather short time (τ < 1 s) from n0 = 0 to n = nf
(where the final chain length of nf > 102–103 units is
limited by the chain termination event) in the case of a
living CRP, each initiation event is accompanied by
only a single polyaddition event and further polyaddi-
tion events necessitate only one reinitiation event for
each polyaddition event. Since Ed ≅ Ei, the situation is
the same as in the step-growth crosslinking polymeriza-
tion of the polycondensation type and the time of prop-
agation (or the lifetime) of polymer chains τp ≥ tf, where
tf is the full time of the polymerization process (as
opposed to the conventional CRP, where the time of
propagation of polymer chains τ < 1 s  tf). Therefore,
it is advisable to regard the living CRP as a peculiar
case demonstrating features of both step-growth
crosslinking polymerization and the conventional CRP.
The above classification performed in terms of the
instantaneous (chain, τ  tf) or slow (step-growth, τp ≥
tf) propagation of polymer chains plus the free-radical
or molecular character of the polyaddition reaction
seems to be the most expedient because of the follow-
ing reasons.
POLYMER SCIENCE Series C Vol. 49 No. 4
337
The side reaction hampering the branching of chains
is the formation of small rings through the interaction
of reactive groups of neighboring chains owing to intra-
chain interactions. As is shown below, in the case of
step-growth and radical-chain polyaddition reactions
may be minimized with the use of substantially differ-
ent methods.
The maximally possible yield Clim of the target
product (HBP) in the synthesis reactions is determined
by a number of parameters (the functionality of the
(1) predicted via calculations using formulas of gelation
theory. In the case of step-growth polyaddition reac-
tions, the well-known Flory–Stockmayer theory is
employed. A quite different approach is required in the
tion theory is used that is specially intended for CRP.
The methods used to govern the synthesis of HBPs
in the case of step-growth and radical-chain polyaddi-
tion also appear to be appreciably different. For the
step-growth formation of growing chains, the control-
ling factors are temperature and sometimes catalyst
additives. In the case of radical-chain reactions, these
(2) factors may be supplemented by the inertia-free control
via external radiation with light or ionizing radiation
(photo- or radical initiation of chains) and through the
addition of special additives, i.e., regulator compounds
(inhibitors, decelerators, chain-transfer agents, and
chain-transfer catalysts).
SYNTHESIS OF HBPS WITH THE USE
OF STEP-GROWTH CROSSLINKING
POLYMERIZATION METHODS
The step-growth crosslinking polymerization
(SCP)2 is the simplest method for the synthesis of
HBPs in terms of the topological mechanism governing
the formation of the cascade of branches, especially if
the AB2 monomer serves as the starting compound.
AB2 monomers possess two substantial advantages.
First, branches emanating from both B groups of the
starting AB2 molecules carry only single-type groups B
incapable of interactions with each other and the forma-
tion of cyclic moieties that are regarded as structural
defects in the case of HBPs. Only one branch emanat-
ing from group A contains a pair of functional groups A
and B that are capable of cyclization. Evidently, the
probability of cyclization will decrease from one gener-
ation to another as a result of the increase in the number
of groups B with the number of groups A being con-
2 Inthe literature, SCP is often referred to as crosslinking polycon-
densation (CP); however, it is more correct to denote only poly-
addition processes accompanied by the release of low-molecular-
mass products (e.g., H2O) using the term CP. Then, the SCP
notion will include step-growth reactions of two types: CP and
polyaddition reactions proceeding without the release of H2O or
other products (urethane formation, Michael’s reaction).
2007
338 KOROLEV, BUBNOVA
stant and equal to unity, independent of the generation
number.
Secondly, as follows from the well-known Flory–
Stockmayer gelation theory, for the SCP of AB2 mono-
mers, the critical conversion (the gel point) Ccr is higher
than the current conversion of C up to the full consump-
tion of the monomer, that is, in the course of SCP C <
Ccr throughout the process; therefore, there is no risk
that gelation, which confines the maximum possible
yield of the target product in the synthesis of HBPs, will
take place. If HBPs are synthesized on the basis of, for
example, binary mixtures of monomers Am + Bn as
starting comonomers (the condition of branching is
m > 2, n > 2, and m + n > 4), in the region of selected
concentrations of Am and Bn, the value of Ccr at certain
m and n may turn out to be much lower than the 100%
conversion and, thus, Ccr will be the limiting factor. The
well-known gelation theories were analyzed by Irzhak
in a review paper [39], including a consideration of the
most rational approaches to the calculation of Ccr val-
ues necessary for the prediction of the maximally pos-
sible yields of HBPs for different synthetic reactions.
The main drawback of the AB2 monomers is the
complexity of their synthesis. As a consequence, these
compounds are inaccessible for the commercial pro-
duction from the viewpoint of economy and engineer-
ing, especially when the matter concerns a wide scope
of diverse AB2 monomers necessary for designing
HBPs useful for certain practical applications.
In the last decade, an original approach was devel-
oped that includes as if one-step reactions of HBP syn-
thesis that actually proceeds via the two-stage mecha-
nism. At the first stage, the binary mixture quantita-
tively transforms into the AB2 monomer and the second
stage involves the synthesis of HBPs, where a change in
synthesis conditions, for example, an increase in tem-
perature, gives impetus to the onset of the second stage.
The main advantage of this approach is that rather
cheap starting compounds are used that are, as a rule,
produced on commercial scale and that a wide range of
HBPs may be synthesized.
Below we will discuss the most interesting variants
of the synthesis of various HBPs based on the use of
SCP methods, including those realized on commercial
scale.
Synthesis on the Basis of Monomers
of the AB2 and ABn types (n = 3–6)
The step-growth crosslinking polymerization of the
AB2 monomers via the esterification, transesterifica-
tion, ring-opening polymerization (including epoxy
addition), and hydride-transfer migration polymeriza-
tion (including urethane formation, Michael’s reaction)
has been in wide use and is being used for the synthesis
of HBPs. This strategy made it possible to synthesize
hyperbranched polyphenylenes [45–48], polyethers
[49–52], polyesters [53–75], polyamides [76–83],
polycarbonates [84], poly(ester ketones) [85–88],
poly(urethanes) [89–94], poly(acetophenones) [95,
96], and poly(carbosilanes) [97–100]. In some cases,
ABn (n = 3–6) rather than AB2 monomers were
employed. In accordance with the Flory–Stockmayer
theory, ABn monomers in which the number of atomic
groups B is larger than two are likewise disinclined to
gelation (as opposed to A2 + B3 binary mixtures and,
especially A2 + Bn mixtures, where n > 3).
Two-Step SCP Including Formation
of AB2 Monomers at the First Stage
The strategy of this approach [101–124] relies on
the use of the A2 + B3 binary mixture for the synthesis
of HBPs. Note that the reactivities of groups A in A2
molecules and groups B in B3 molecules should be sig-
nificantly different so that one of the A groups and one
of the B groups should possess much higher reactivities
in the A + B addition reaction (more reactive groups are
designated as A' and B' and monomers A2 and B3 as
A'A and B'B2, respectively). In this case, it is possible
to select rather mild reaction conditions under which
only reaction A' + B' may proceed, while reaction A +
B occurs at an almost zero rate (as a rule, this is
achieved owing to the use of rather low temperature
T1). Under these conditions, solely the dimeric product
is formed as follows from A'A + B'B2 AB2. After
completion of said stage, which is controlled by con-
version measurements by appropriate methods, the
synthesis conditions become more severe (e.g., the tem-
perature is increased from T1 to T2, which is 20–50°ë
higher than T1) and then AB2 converts into the HBP. It
is obvious that the selective transformation of the A2 +
B3 binary mixture into the A2B monomer will also take
place if in A2, both A groups exhibit equal reactivities
and in B3, both B groups possess enhanced reactivities.
This implies that A2 ≡ A2 and B3 ≡ BB 2' . Then, the
selective interaction A + B' gives rise to the A2B mono-
mer, which also transforms into the HBP and complica-
tions related to gelation appear to be avoided. The only
difference of the A2B monomer from the AB2 monomer
is that the HBP being formed will contain functional
groups A (the A2B monomer) at chain ends or func-
tional groups B (the AB2 monomer).
The most interesting variants of this approach (one-
step in terms of engineering) and the two-step approach
(in terms of the chemical mechanism) were described
in [102–115].
In [102–104, 110–120], the promising variants of
the selective synthesis of AmBn monomers (m + n ≥ 3 at
m = 1 or n = 1) were developed. These monomers can
be converted into HBPs with a high yield (close to
100%) without complications such as gelation. This
synthesis proceeds as a separate initial stage of the one-
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
step process that occurs in in situ Am + Bn binary mix-
tures of ecologically accessible commercial monomers
and allows one to prepare a wide range of HBPs of var-
ious chemical structures of the polymer framework (poly-
esters, polyamides, poly(urethanes), polyureas,
poly(amino amides), and poly(ester amides) and con-
taining diverse end functional groups (hydroxyl, amine,
ester, and multiple bonds). As a result, the characteris-
tics of HBPs may be varied in a wide range, as required
by specific targets.
Even wider possibilities are provided if the number
of components in the starting mixture used for the
selective synthesis of AmBn monomers (m or n is unity,
and m + n ≥ 3) is higher than two. In [116, 121–124],
ternary mixtures were employed for this purpose. The
third component serves as an extender of interjunction
chains in the framework of HBPs.
SCP of A2 + B3 Binary Mixtures
and Other Methods of Preparing HBPs
The employment of A2 + B3 binary mixtures is the
most promising approach for varying the chemical and
topological structure of HBPs. In the previous section,
we considered the case when, because of the different
reactivities of groups B in B3 molecules (or groups A in
A2 molecules), polymerization in fact proceeds via the
mechanism of the homopolymerization of the initially
formed adduct of the AB2 type. If the reactivites of
these groups are equal or similar, the copolymerization
of the A2 + B3 mixture is complicated by gelation [125–
128]. Therefore the synthesis of HBPs is limited by two
factors, namely, the small yield of the target product
and the sharp narrowing of the possible interval of vary-
ing the A2-to-B3 ratio in the initial mixture. Both factors
may be predicted in terms of the Flory–Stockmayer
theory, and were generalized and analyzed in a recent
review [39]. As evidenced by predictions, at the A2-to-
B3 ratios providing a sufficient degree of branching of
copolymers, the critical conversion (the gel point) turns
out to be shifted to the region of very small conversions;
hence, the target product is produced with a very low
yield. Therefore, the synthesis [129] of HBPs on the
basis of A2 + B3 binary mixtures is performed under
special conditions hampering gelation, for example, at
very small total concentrations of the reagents (3.3 wt %)
or in poor solvents ensuring the continuous removal of
the HBPs from the reaction zone via precipitation.
On the basis of A2 + B3 binary mixtures, the authors
of [129–138] managed to synthesize HBPs of chemical
structures that were unachievable by other synthetic
procedures.
Other methods for the synthesis of HBPs via the
SCP method exist, for example on the basis of Bn + AB2
mixtures, where n > 3, and the concentration of Bn is
very small ([Bn]  [AB2]). This was the method used
by Perstorp Specialty Chemicals AB (Sweden) for the
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
339
commercial production of HBPs under the trademark
Boltron. This synthesis is described in detail in the next
section.
The Commercial Synthesis of HBPs
HBPs are currently produced on commercial scale
[11, 139, 140] by two companies, including the Swed-
ish company Perstorp Specialty Chemicals AB, with a
division called Perstorp Polyols Inc. (USA), and DSM
Fine Chemicals (Holland). The HBPs produced by Per-
storp are known under the general trademark Boltorn,
while those manufactured by DSM, are known as
Hybrane. All HBPs of the Boltorn family contain the
same framework (the chemical structure of aliphatic
polyesters) and differ in the number of generations (2–5)
and Mw = (2.1–14) × 103. The type of end functional
groups in series H20, H30, H40, and H50 (the first figures,
2, 3, 4, and 5, are generation numbers) is also the same
(OH). Therefore, this series may be regarded as basic.
Polymers of this series may easily be modified via the par-
tial or full replacement of hydroxyls with other functional
groups, for example, through their esterification. Thus,
modified HBPs are also produced by Perstorp, while their
polymer framework remains unchanged.
DSM produces a wider range of HBPs in which not
only a set of end functional groups, but also the chemi-
cal structure of the framework, was modified. It was
found that this modification affects the properties of
HBPs as much as the set of functional groups.
According to the Perstorp method, HBPs are synthe-
sized from the binary mixture pentaerythrite + 2,2-dim-
ethylolpropionic acid (the B4 + AB2 system) via the
esterification reaction. In some cases, trimethylolpro-
pane (B3) is used as a mutiatomic alcohol.
DSM accomplishes synthesis in a different way,
namely, via the crypto-two-step process (see the section
entitled “Two-Step SCP Including Formation of AB2
Monomers at the First Stage”). A binary mixture com-
posed of anhydride of dibasic carboxylic acid and
aminediol is used. These compounds interact to form an
adduct containing two hydroxyl groups and one car-
boxyl group (the AB2 monomer). Then, the AB2 mono-
mer formed in situ via the esterification mechanism
transforms into the HBP. The first stage proceeds under
mild conditions consisting of moderate temperature
and the absence of evacuation and catalyst additives.
After the completion of the first stage (according to the
spectroscopic control of conversion), the reaction con-
ditions become more severe; temperature is elevated,
evacuation begins, and the equilibrium of esterification
is shifted via the removal of H2O from the reaction sys-
tem; sometimes, small amounts of esterification cata-
lysts are added. Thus, the second stage of the synthesis
of HBPs from the AB2 being formed is initiated. The
chemical structure of the polymer framework of HBPs
is changed within the following set of the starting anhy-
drides: cyclohexanedicarboxylic anhydride, siccine
340 KOROLEV, BUBNOVA
anhydride, phthalic anhydride, and siccine anhydride
with various substituents; the end functional groups
vary within the following set: residues of fatty acids,
benzoic, methacrylic, and functionalized acids.
SYNTHESIS OF HYPERBRANCHED POLYMERS
BY CROSSLINKING RADICAL
POLYMERIZATION METHODS
The main advantage of radical polymerization that
the propagation of macromolecules obeys the chain
mechanism appears to be its main disadvantage for the
synthesis of HBPs. Actually, on the one hand, the chain
mechanism ensures a high rate of the process, good
controllability through variations in the concentrations
of initiator, inhibitor, and chain-transfer agent addi-
tives, extremely high predictability on the basis of a
large data array on the rate constants of elementary
stages kel accumulated to date owing to the continuous
development of new and accurate methods of their
experimental measurements and the creation of suffi-
ciently reliable determination of kel via calculations
[141] with due regard for a number of universal features
inherent to radical reactions, plus the elaboration of a
new theory of gelation intended especially for
crosslinking radical polymerization (CRP). On the
other hand, owing to the chain mechanism, the ten-
dency toward transition from the formation of branched
polymerization products (soluble HBPs) to both infus-
ible and insoluble network polymers (micro- and mac-
rogels) is extremely high. Thus, for example, the criti-
cal conversion Ccr (in other words, the gel point) at
which the polymer system transforms into a gel, in the
case of the radical polymerization of (meth)acrylic
monomers å2 containing two multiple (polymerizable)
bonds each, is shifted to the region of small conversions
Ccr 0 to such an extent that at conventional rates of
initiation wi
10–6–10–8 mol/l, this parameter may be
measured experimentally with an accuracy equal only to
its upper boundary Ccr < 0.01. More accurate calculation
of Ccr with the gelation theory formulas [10, 35–39] yields
Ccr
10–4. In other words, under conventional conditions,
HBPs synthesized through CRP may be formed with a
yield smaller than 1%. If an even more polyfunctional
monomer than å2 is used as the starting monomer for the
synthesis of HBPs, for example Mm (where m > 2), the
value of Ccr turns out to be even smaller.
As follows from the gelation theory [10, 35–39], the
value of Ccr (and, hence, the yield of HBPs) may be
increased by changing the conditions of CRP via two
directions; namely, a decrease in the mean functionality
Φ of the starting monomers and a decrease in the length
P of propagating polymer chains (in this case, P is the
number of units, that is, the length of substantial chains,
as opposed to the length of kinetic chains ν).3 In order
3 Additivesof chain-transfer agents only reduce the value of P and
have no effect on the value of ν.
to decrease Φ in the case of å2 molecules, å2 should
be diluted with monounsaturated (non-network form-
ing) monomer å1 carrying only a single polymerizable
double bond. However, in this case, there is the restric-
tive condition relative to the mixture composition
[å2]/[å1]; namely, as dilution with monomer å1
achieves such a level that the content of å2 becomes
less than 3 in chains composed of P units, the degree of
branching in the HBP being formed becomes smaller
than 2 and further dilution leads to the formation of
weakly branched polymers lacking the properties of
HBPs. With the example of a mixture of monomers
å1 + å2 of the (meth)acrylate type, it is readily seen
that, at conventional wi
10–7 mol/(l s), the value of
P
104 units and Ccr 1 (accordingly, the yield of
HBPs 100%), at the molar composition of the mix-
ture [M2]/[M1] 10–5. Hence, if dilution with mono-
mer å1 is performed to such an extent that the yield of
the soluble polymerization product will increase to
100%, then this product will be practically unbranched
(each chain composed of 104 units will contain on aver-
age 0.1 unit of the branching monomer å2).
As the degree of dilution is reduced to [å2]/[å1] =
3 × 10–4 providing a degree of branching equal to 2, Ccr
decreases to 0.1 (the yield of HBPs is as low as 10%).
Even if such a small yield will suffice, one should still
bear in mind that the HBP being formed will differ
appreciably in terms of topology from the typical HBPs
that have been synthesized and characterized thus far.
This topological difference is that chain fragments
between neighboring branches (the so-called interjunc-
tion chains) will be very long; namely, on average, two
branches per chain of length P = 104 units, that is, the
length of interjunction chains will be close to 103 units.
The synthesis and characterization of HBPs with varied
lengths of interjunction chains demonstrated [142] that
at a length exceeding several tens of units, the proper-
ties of HBPs become close to the properties of conven-
tional linear polymers of similar molecular masses.
Therefore, for the synthesis of HBPs via radical
polymerization, the approach based on the dilution of
polyfunctional monomers Mm with mononfunctional
monomers M1 is used only additionally, while the basic
approach includes the development of methods allow-
ing one to decrease the value of P to a few units.
In the following, we will describe the most efficient
approaches of this type that make it possible to advan-
tageously synthesize HBPs via radical polymerization
methods.
Control of Chain Length through Variation
in the Rate of Initiation
As follows from the theory of chain reactions, the
length of chains decrease with an increase in the rate of
initiation wi. Calculations showed that P
3 may be
attained if, instead of usual concentrations of the initia-
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
tor [I] ≤ 10–2 mol/l, this value is increased at least by
two orders of magnitude, that is, [I] should be ≥ 1 mol/l,
which is commensurable with the concentration of
monomers.
It is obvious that the HBPs synthesized under the
given conditions will inevitably contain a large amount
of initiator fragments in both interjunction and end
chains.
This method was first advantageously employed by
Sato et al. [8, 143–148] in 2002–2004 from the
å2 monomers of the dimethacrylate and divinylben-
zene types (sometimes in the case of dilution with å1)
in the presence of dimethyl-2,2-azo-bis(isobutyrate)
(DABIB) (sometimes with inhibitor additives). These
authors designated this synthesis of HBPs as the initia-
tor-fragment incorporated radical polymerization.
Well-characterized (with the use of modern methods
of studying HBPs) products were prepared via the
DABIB-initiated copolymerization of divinylbenzene
(å2) with ethylstyrene (å1) in the presence of ben-
zoyliminoacetate as a retarding agent at 70–80°ë (the
time of full conversion is tc = 8–24 h) [143] and the
DABIB-initiated copolymerization of ethylene glycol
dimethacrylate (å2) with N-methylmethacrylamide
(å1) at 70–80°ë (tc = 1–12 h) with a yield of 46–50%
[147]. Along with divinylbenzene [145] and ethylene
glycol dimethacrylate [144, 148], divinyl adipate [8,
146] was used as the branching agent å2.
At present, there is no way to evaluate the impor-
tance of Sato’s method for its practice and competitive-
ness since it is unclear [8, 143–148] what the labor
expenditures and complexity of isolation of HBPs are
from the 50% mixture of their byproducts. Evident
drawbacks of the method under examination are that
the synthesis should be carried out in very dilute solu-
tions and the consumption of the initiator is large. Cer-
tain advantages of the above method are its universal
character and high rate of the process. The universal
character is that the method allows one to prepare HBPs
that contain any type of functional groups since the
assortment of components of radical copolymerization
å1 and å2 is large. For example, only one class of å1
monomers, such as methacrylates of formula
CH2=C(CH3)COOR, includes compounds that bear dif-
ferent radicals R ranging from alkyls with widely var-
ied lengths and degrees of branching of carbon chains
to R-containing atomic groups –OH, –NH2, and
HC CH2 and methacrylates containing atomic
O as a catalyst.
groups –C(O)NH2 and –COOH (methacrylamide and
methacrylic acid).
Control of Chain Length with the Use
of Chain Transfer and Catalytic Chain Transfer Agents
Another way of decreasing the length of chains to
values acceptable for the synthesis of HBPs is the inten-
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
341
sification of chain-transfer events. This approach was
used extensively by a group of English researchers
under the guidance of Sherrington [149–153]. Chain
transfer was performed via two methods, namely, tradi-
tional and nontraditional. The traditional method
includes the addition of small amounts of compound Tr
capable of reacting with prapagation radical R to gen-
erate a new, also active, radical Rtr, initiating a new sub-
stantial chain. In this case, molecules Tr are lost and,
hence, the consumption of Tr is 1 molecule per chain.
Calculations show that P = 3–5 may be attained, the
values of ktr[Tr] should be lower than the values of
kp[M] by only a factor of 3–5 (at conventional initiation
rates, wi
10–7 mol/(l s) in the absence of inhibitors).
Here ktr and kp are rate constants of chain transfer and
chain propagation, respectively. In other words, either
high ktr > kp (at small [Tr]  [M]) or, at ktr < kp, large
[Tr] commensurable with [M] are necessary. Variant
ktr > kp is highly inconvenient for the synthesis of
HPBs. It can be readily seen4 that the consumption of
Tr in this case will be faster than the consumption of M
and that a continuous supply of Tr in the course of poly-
merization is required in order to maintain P = constant.
Hence, it is expedient to employ extremely high con-
centrations of Tr or the nontraditional approach, which
relies on the use of chain-transfer catalysis. This phe-
nomenon was discovered more than two decades ago
[7, 154] and has found extensive use in world science
and practice.
Sherrington et al. employed both approaches,
namely, the traditional method based on the use of high
concentrations of Tr and the chain-transfer catalysis,
for the synthesis of HBPs via the crosslinking radical
(co)polymerization.
The chain-transfer catalysis was discovered for the
polymerization of methyl methacrylate in the presence
of very small (catalytic) amounts of organic macrocy-
clic complexes of cobalt CoL (cobalt porphyrins and
phthalocyanines and cobaloximes). It was found that
CoL added in the amount of 10–6–10–5 mol/l decreases
the length of chains by a factor of 10–100. This case
corresponds to ratio ktr
kp. However, at ktr
kp, the
action of CoL would have already ceased at the very
beginning of polymerization because of the faster con-
sumption of CoL than of M. However, this was not the
case. CoL functioned throughout the polymerization,
was not consumed in this process (as evidenced by
measurements of ån values for polymers isolated at
various stages of polymerization), and, hence, behaved
4 The d[M]
solution of a system of differential equations – ------------- =
dt
. d [ Tr ] . k tr /k p
kp[M][ R ] and – ------------- = ktr[Tr][ R ]; [Tr] = [Tr]0 – (1 – C) ,
dt
[ M ]0 – [ M ]
where C = ---------------------------- yields conversion of the monomer.
[ M ]0
342 KOROLEV, BUBNOVA
On the basis of the comprehensive study [155] of
chain-transfer catalysis by various methods (GPC and
NMR, IR, and UV spectroscopy), the following mech-
anism of catalysis was proposed
. –R
. 20–30 C atoms (according to our calculations on the
R + CoL [RCoL] [HCoL] CoL + H
. .
H+M R.
The polymethacrylate chain R, containing an end dou-
CH2
ble bond of the CH2 C type that differs from
COOCH3
CH3
the methacryl double bond CH2 C COOCH3 , is
formed via the disproportionation of the propagation
. merization and may serve as objects of further modifi-
radical R accepted by CoL as a complex [RCoL], fol-
lowed by transformation into CoL hydride. The latter
compound is extremely instable and decomposes
almost instantaneously to afford atomic hydrogen and
. tion of HBPs of this type. However, the prospects of
the starting CoL. The resulting H is extremely active
. their synthetic procedure is rather simple. This is evi-
and instantly generates a new chain R .
Further developments in the field of chain-transfer
catalysis [156] led to the design of new, more efficient
complexes of CoL, as well as to the elaboration of
numerous practical applications for this phenomenon.
The approach, employed by Sherrington et al., was
based on the intensification of chain transfer via both
methods, namely, the use of high concentrations of Tr
(dodecylmercaptane) and chain-transfer catalysis. As
branching monomers åm (where m = 2 or 3), di- and
tri(meth)acrylates, and divinylbenzene were tested,
while methyl methacrylate was used as å1 [149–153].
The temperature of copolymerization was 70–80°ë.
The concentration of conventional initiator (AIBN) was
~5 × 10–2 mol/l. The value of wi was estimated as 5 ×
10–7 mol/(l s) typical of radical polymerization pro-
cesses. Weakly polar solvents (as a rule, toluene) were
taken at a concentration of ~60 vol %. The yield of
copolymers achieved within 16 h was ~90%. The con-
centration of Tr in all experiments was equal to the con-
centration of å2. The values of ktr (l/(mol s)) were
~300 and ~3500 for methacrylates and acrylates,
respectively. The values of kp were ~500 and ~2000,
respectively. When Tr was replaced with a chain-trans-
fer catalyst (a complex of BF3 with cobalt cobaloxime),
the effective value of ktr increased to (1.5–2.0) ×
107 l/(mol s). Therefore, very small additives of the cat-
alyst (smaller than [Tr] by a factor of 105) turned out to
be efficient.
A wide assortment of copolymers with properties
typical of hyperbranched polymers has been synthe-
sized. This fact gives us grounds to class them as HBPs.
As was shown to be typical of HBPs in [142], as the
length of interjunction chains is increased to 10–15 car-
bon atoms, the properties inherent to HBPs disappear.
In the case of the copolymers synthesized by Sher-
rington et al., the length of interjunction chains is above
basis of ktr[Tr]). It is suggested that the topological
structure formed under the conditions of radical copo-
lymerization in å1 + å2 + Tr system is a new type of
HBP.
Systematic series of HBPs have been prepared
through a targeted variation in their parameters (molec-
ular mass, generation number, degree of branching, and
functionality) and the effect of these factors on the
characteristics of these polymers has been elucidated.
As main functional groups, double bonds were detected
in all cases; as a result, the HBPs thus prepared demon-
strate well-pronounced reactivity in radical (co)poly-
cation, for example, via the addition of amines accord-
ing to Michael’s reaction.
There are no data concerning the practical applica-
their commercial production seem to be quite real since
dent from the papers by Sherrington et al. published in
2006 that are devoted to the development of the synthe-
sis of HBPs through the copolymerization of methyl
methacrylate and divinylbenzene in aqueous emulsions
[157]. It appears that the use of water instead of inor-
ganic solvents as a reaction medium will noticeably
improve the engineering effectiveness of the process
(ecological and fire safety and economy).
Synthesis of HBPs Based on Intrachain Reactions
of Propagation Radicals Terminating Growth
of Polymer (Substantial) Chains
As was shown recently, in addition to the known
reactions of chain transfer, other nontrivial radical reac-
tions that also cause termination of the length of poly-
mer chains may occur during radical polymerization.
The first signs of these reactions were discovered
very long ago during the study of the thermal (in the
absence of substantial initiators) polymerization of sty-
rene [158–161]. However, the detailed mechanism of
these reactions that was later used for the synthesis of
HBPs [162] has been ascertained most recently [163]
with the use of a combination of several analytical pro-
cedures, including, along with GPC and 13C NMR spec-
troscopy (300 MHz), the newest variant of mass spec-
trometry (MALDI TOF). As a result, for the polymer-
ization of styrene at 260–340°ë, the molecular mass
distributions of the products were estimated and both
end groups of oligomer chains were identified.
An examination of the chemical structure of all
polymerization products (including the identification of
the end groups of oligostyrenes) revealed that for the
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
high-temperature polymerization of styrene, the intrac-
hain attack of the end propagation radical at the fifth
carbon atom accompanied by the elimination of H
(attack at the third carbon atom is also possible) is the
main mechanism governing the termination of growing
polymer chains. Furthermore, it was shown [164–167]
that polymer chains carrying end double bonds are able
to react with the propagation radical according to the
so-called addition–fragmentation mechanism.
The contribution of new reactions involving self-ter-
mination of the length of polymer chains growth with
the temperature of polymerization. It was demonstrated
[162, 168–170] that if the time τ of residence of
reagents in the reactor is time properly selected, poly-
merization may be performed at such a high tempera-
ture (260–340°ë) that on one hand, polymers consist-
ing of supershort chains (less than 10 units) may be
synthesized and, on the other hand, side reactions of the
high-temperature chemical degradation of polymers
and monomers have no time to develop. Evidently, the
flow reactor is the most convenient type of reactor with
a controlled value of τ. The above data were used as
basis to develop the method of synthesis of HBPs
through the high-temperature copolymerization of sty-
rene and divinylbenzene (DVB) [162, 168–170]. The
synthesis of HBPs was performed in the flow reactor.
Optimal conditions of synthesis were selected through
variations in temperature, time, and concentration
(c2, wt %) of DVB (the commercial mixture of 80%
p-DVB and m-BMN with 20% styrene) and the concen-
tration of a solvent (0–15% of aromatic hydrocarbons
with a boiling temperature of 100°ë). The value of c2
was selected from the dependence of Mw of the polymer
on c2, while other conditions remained invariable
(Unfortunately, the values of Mw were estimated only
by GPC-1 with the use of a refractometric detector and,
therefore, cannot be regard as strictly quantitative.).
The approach to critical conversion Ccr (the gel point)
manifests itself as a sharp rise in the rate of an increase
in Mw with c2. On the basis of special GPC measure-
ments of sol fractions, the approach to Ccr was judged
from the change in the sign of the first derivative of
function Mw = f(c2) from plus to minus at a certain con-
centration of the branching monomer. This concentra-
tion (0.106 wt % DVB at 316°ë, τ = 15 min, and 15 wt
% solvent) was assumed as the critical conversion Ccr
(the gel point).
In [162], systematic data concerning the effect of
copolymerization conditions controlling the value of
Mw of the copolymers were obtained as several series of
Mw = f(c2) curves. Evidently, this evidence may serve
as a basis for both the optimization of the synthesis of
HBPs and the prediction of its results at preset condi-
tions of copolymerization.
Measurements of molecular-mass distributions of
the copolymers showed that for all degrees of branch-
ing, molecular-mass distributions are broad and contin-
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
343
uously widen with the degree of branching (with an
increase in c2). With due regard for the fact that the
GPC-1 technique (without light scattering detector)
yields underestimated results because of reduced
hydrodynamic volumes of branched macromolecules
compared to their linear analogs of the same molecular
mass. It should be expected that, in fact, the molecular-
mass distributions of the copolymers will be even wider
owing to a shift to the high-molecular-mass region.
The authors of [162, 168, 169] demonstrated that
their method of synthesis of HBPs is highly economical
quite competitive and may used on the commercial
scale. However, information concerning the valuable
and useful properties of the HBPs of this family at least
the published data is absent.
LIVING RADICAL POLYMERIZATION
AS A REACTION OF SYNTHESIS OF HBPS
Living chain mode in radical polymerization signif-
icantly affects the mechanism of the propagation of
macromolecules and changes it from chain (instanta-
neous) to step-growth (slow). “Instantaneous” implies
that the time of chain propagation τ from nucleation
(initiation) to termination (irreversible termination, lin-
ear or bimolecular) is incommensurably small com-
pared to the time of development of polymerization tf
from the zero to final conversion; that is, τ  tf. There-
fore, polymerization proceeds as accumulation during
the tf of chains of certain lengths ν formed instanta-
neously (τ  tf) after each initiation event and the cur-
rent rate of polymerization w is expressed as the prod-
uct of the current rate of initiation wi by the current
chain length ν as follows:
w = wiν.
The term “slow” means that the mean time of chain
propagation from nucleation to irreversible termination
τ is commensurable with tf (usually τ ≥ tf). In other
words, chains lengthen continuously in the course of
polymerization and a gain in conversion is achieved not
due to the accumulation of chains of certain lengths ν,
but rather due to the summation of gains in the lengths
of all chains nucleated at practically the same time at
t 0 (instantaneous initiation). More importantly,
each event of chain propagation is characterized by a
high activation barrier Eν that is comparable with the
activation barrier of the elementary event of chain initi-
ation Ei, that is, Ei
Eν. Therefore, each event of chain
gain takes place only after the reinitiation event. In this
sense, in fact, the chain propagation of macromolecules
is identical to the step-growth polyaddition reaction, for
example, polycondensation and migration polymeriza-
tion.
Since the step-growth polymerization (polyconden-
sation) of AB2 monomers is the simplest variant of the
synthesis of HBPs, living radical polymerization is per-
344 KOROLEV, BUBNOVA
spective for the production of these polymers on condi-
tions that the starting unsaturated monomer that will
polymerize, similarly to AB2, is synthesized (prelimi-
narily or in situ, directly in the (co)polymerization sys-
tem).
The use of formulas from [10, 35–39] for the deter-
mination of the critical conversion Ccr for the living rad-
ical (co)polymerization process shows that the simple
combination of a monounsaturated monomer (å1) and
a branching (multiunsaturated) comonomer åm (m is
the number of double bonds in a molecule) provides no
way of synthesizing HBPs via living radical polymer-
ization. Despite a well-defined step-growth character of
the latter process, the value of Ccr turns out to be inad-
missibly small (Ccr < 5%), provided that the degree of
branching of the copolymers is reasonable. At more or
less acceptable values of Ccr < 50%, the degree of
branching of the copolymers is so small that they can-
not be classed as HBPs.
In 1995, Hawker and Frechet et al. [171–173] first
synthesized the AB2 monomer capable of living radical
polymerization. The monomer prepared by those
authors underwent polymerization at 120–130°ë by the
living radical mechanism, as with AB2, owing to the
reversible hemolytic dissociation of a NO–C bond and
the subsequent step-growth addition of the carbon-cen-
tered radical to the double bond of the next monomer
molecule. These reactions are well known and have
been studied in detail within the framework of the so-
called alkoxyamine mechanism of living free-radical
polymerization [6].
In 2000, Voit reported on the original variant of liv-
ing radical polymerization suitable for the synthesis of
HBPs [174]. As the starting AB2 monomers, Voit used
compounds capable of generating free radicals under
the action of UV radiation and these radicals served as
reversible inhibitors.
Considerable progress in the field of the synthesis of
HBPs through the living radical polymerization of
functionalized styrenes was achieved for styrenes con-
taining CH2–S–C(S)N(C2H5)2 substituents in para posi-
tions (see the next section).
The synthesis of HBPs via the living free-radical
polymerization of functionalized acrylates and meth-
acrylates is based on the monomers whose synthesis
was described in [175–185].
According to the authors of numerous recent
reviews concerning HBPs, the syntheses of HBPs from
the functionalized monounsaturated monomer contain-
ing functional groups involved in formation of branches
may be united in a separate class of self-condensing
vinyl polymerization reactions. This term is used so fre-
quently that its abbreviation, SCVP, often remains
unclarified. However, since self-condensation may fol-
low different mechanisms, we consider this classifica-
tion unjustified and will not use it.
SYNTHESIS OF HBPS
AND NANOSTRUCTURED POLYMERS
VIA LIVING RADICAL POLYMERIZATION
OF VINYL MONOMERS
WITH DIETHYLDITHIOCARBOMATE ATOMIC
GROUPS
This direction of synthesis of HBPs turned out to be
extremely fruitful and allowed the strategy of the syn-
thesis of hyperbranched macromolecules of compli-
cated topological architecture to be developed. These
polymers are referred to as “nanostructured.” These
materials have found use in the up-to-the-minute fields
of engineering, for example, in microelectronics in
combination with Aq or Cu nanoparticles as polymer
plasmons. Otsu et al. [186–188] is the father of living
radical polymerization that relies on the use of com-
pounds with dithiocarbamate groups. The main results
of the long-term observations of this group of Japanese
researchers were summarized in two reviews [189,
190].
On the basis of the above result, another group of
Japanese researchers headed by Ishizu elaborated a new
strategy for the synthesis of HBPs [191–204]. They
synthesized stryrene and methyl methacrylate carrying
N,N-diethylaminodithiocarbamoyl (DC) groups as
starting monomers.
The photopolymerization (UV radiation) of these
monomers in 50% solutions in benzene, which pro-
ceeds according to the living radical mechanism as
established by Otsu [189, 190], allows one to synthe-
size hyperbranched polystyrene and poly(methyl meth-
acrylate) containing DC end groups.
Since, according to Otsu’s mechanism, chains con-
taining DT end groups are living, they may be used for
their further lengthening via the addition of small
amounts of any other vinyl monomers after the com-
plete consumption of the starting monomers. As a con-
sequence, on the basis of primary HBPs, one may syn-
thesize secondary nanostructured polymers, for exam-
ple, star-shaped, nanosized macromolecules containing
long grafted chains [193, 198], nanocylinders [192],
and other nanostructured polymers of complicated
topological architecture [191]. In some case, the
synthesis of these polymers does not require photopo-
lymerization as the first stage of the process. Under
photoirradiation, DC groups undergo reversible disso-
ciation and, thus, inevitably form a branched macro-
molecule. When a linear starting macromolecule carry-
ing living propagation sites and carbochains framework
is required as an intermediate product to produce a
nanostructured polymer (the case of nanocylinder),
dark polymerization is carried out at the first stage in
the presence of conventional initiators (e.g., 2,2'-azo-
bis(4-methyl-2,4-dimethylvaleronitrile)) as in [192]
and then the photopolymerization of the obtained pre-
polymer is performed in the presence of any other
monomer selected for the formation of a given nano-
structure. Another advantage to the approach under
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
consideration is that DC groups as agents of living rad-
ical polymerization are insensitive to the nature of dou-
ble bonds in vinyl monomers, as opposed, for example,
from alkoxyamines. The universal character of DC
groups allows one to combine the above-mentioned
monomers with vinyl monomers containing any func-
tional groups (hydroxyl, carboxyl, amine, amide) in the
synthesis of HBPs and, thus, to incorporate these
groups into the resulting macromolecules.
This method was employed by Ishizu et al. for the
synthesis of hyperbranched polystyrenes [202, 203],
HBPs composed of alternating styrene–maleinate [199]
and styrene–maleimide [197] units, and hyperbranched
polymethacrylates [194, 195, 204]. The synthesis of
HBPs with complicated molecular architecture (nano-
structured polymers) was described in [191–193, 200].
Macromolecules of the nanocylinder type containing
side hyperbranched side chains were synthesized in
[192].
In [200], the modification of HBP, synthesized
through the photopolymerization of diethyldithiocar-
bamate styrene-substituted monomer, was used as a
prefrepolymer for further photopolymerization in the
presence of 1-vinyl-2-pyrrolidone. The amphiphilic
HBP thus prepared is characterized by a complicated
topological architecture and consists of hydrophilic
branched chains and a hydrophobic framework.
In [193], the HBP synthesized through the photopo-
lymerization of the same monomer was modified via
grafting of poly(tert-butyl methacrylate) chains and
subsequent hydrolysis of ester groups. The as-prepared
graft HBP having long chains with carboxyl groups
represented star-shaped nanospheres with strongly
polarized arms. Further complication of this nanostruc-
ture was accomplished via electrostatic interaction with
poly(4-vinylpyridine) and partially quaternized poly(4-
vinylpyridine).
The authors of [198] described the synthesis of lin-
ear hydroxyl-containing chains carrying living end
groups via the UV-photopolymerization of 2-hydroxy-
ethyl methacrylate in the presence of 2-(N,N-dieth-
yldithiocarbamoyl)isobutyric acid as a photoinitiator.
The resulting hydrophilic chains containing OH groups
in each unit and end DC groups are suitable as struc-
tural elements for the synthesis of topologically com-
plex macromolecules.
Many examples illustrating the chemical engineer-
ing of such macromolecular structures were surveyed
in [191]. Special attention was given to structures
(HBPs and nanostructured polymers of the rigid rod
type and brushlike shape), which remain nonaggre-
gated, even in very concentrated solutions. This ability
to remain as individual macromolecules is extremely
valuable and necessary for both injection molding
(polymer additives that do not worsen the rheological
characteristics of the starting uncured compositions)
and in modern engineering (nanocapsules for Ag and
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
345
Au particles in polymer plasmons and homogeneous
distribution of particles in nanocomposites).
It should be emphasized that all HBPs and nano-
structured polymers synthesized by Ishizu et al. are
characterized by a set of the newest methods; all possi-
ble molecular parameters were characterized and their
properties were thoroughly studied.
SYNTHESIS OF HYPERBRANCHED
POLYMERS WITH OXYGEN-CONTAINING
FUNCTIONAL GROUPS
THROUGH RADICAL POLYMERIZATION
IN THE PRESENCE OF OXYGEN
Oxygen is an extremely efficient acceptor of carbon-
centered free radicals. The rate constant of the reaction
depicted below lies within kx = 106–107 l/(mol s)
. kx .
R + O2 RO 2 . (8)
In the case of the radical polymerization of vinyl mono-
mers, é2 plays the role of an inhibitor whose efficiency
depends on the reactivity of the double bond of a given
.
monomer with respect to radical RO 2 . As a rule, the
numerical value of the rate constant for reaction (9) is
lower by a factor of 10–100 than the rate constant k of
reaction (10);
. k2 .
RO 2 + M R, (9)
. kp .
R+M R, (10)
.
where R is the carbon-centered radical. It is evident
that the lower the value of k2/kp, the higher the effi-
ciency of O2 as an inhibitor. At k2/kp = 1, the inhibiting
effect of é2 disappears. At k2/kp < 1, the presence of
oxygen in the polymerization system decreases the
chain length and may be used for this purpose in the
synthesis of HBPs instead of chain transfer agents, such
as macrocyclic complexes of cobalt, and, moreover,
instead of other methods of chain shortening described
in previous sections.
Furthermore, the processes that are referred to as
radical-initiation oxidation of vinyl monomers occur in
the polymerization system in the presence of oxygen.
These processes have been well studied (e.g., mono-
graph [205]) and are assumed to be responsible for the
appearance of oxygen-containing functional groups in
the polymers, such as COH , –C(O)OH, COOH ,
C O C , C OO C , aldehyde, and ketone
moeities.
Finally, if oxygen is present in the polymerization
system, compounds functioning as radical-chain initia-
tors (peroxides and hydroperoxides) are formed. As a
346 KOROLEV, BUBNOVA
result, either the necessity of using conventional initia-
tors is sharply decreased or there is no need to use them
at all.
Hence, the employment of atmospheric oxygen,
which is the most assessable and cheap reagent, for the
synthesis of HBPs makes its possible to simultaneously
control the chain length (and, accordingly, the degree of
branching) and to incorporate oxygen-containing func-
tional groups into HBP macromolecules (plus reduc-
tion in the amounts of the initiator or its abandonment).
The first syntheses of HBPs via the polymerization
of polyunsaturated monomers were performed as early
as the beginning of the 1970s [206–209] during the
kinetic and mechanistic study of oxidative polymeriza-
tion process. This direction of polymer science was cre-
ated under the guidance of Mogilevich and developed
for several decades. As polyunsaturated monomers,
unsaturated acrylic oligoesters containing two, four,
and six double bonds per molecule were used. Poly-
merization was carried out in bulk at 80–100°ë for 40–
100 min to give rise to soluble products with a yield of
20–50%. The study of these products by means of IR
spectroscopy, high-resolution 1H NMR spectroscopy,
and chemical analysis showed that these are branched
macromolecules containing (per monomer unit) 0.5–
2.0 molecules of added oxygen (up to 0.5 molecules per
reacted double bond) and up to two or more double
bonds and 0.2–0.8 carboxyl groups. With a high degree
of probability, it may be stated that HBPs were synthe-
sized. However, valuable properties of hyperbranched
polymer structures had not been discovered at that time.
Therefore, the above products have not been character-
ized by specific procedures currently available for the
identification of HBPs.
The strategy of the synthesis of HBPs in the pres-
ence of atmospheric oxygen was developed at the Insti-
tute of Problems of Chemical Physics, Russian Acad-
emy of Science under the guidance of Korolev on the
basis of the mathematical model proposed for the
crosslinking oxidative polymerization of styrene and
methacrylate monomers.
The conditions of polymerization (temperature,
concentration of monomers, solvent, and type and
amounts of initiator) are selected on the basis of calcu-
lations performed in terms of the mathematical model
of the process. The base data for the mathematical
model are the rate constants (or their combination) of
elementary stages of polymerization [210–212], oxida-
tive polymerization [205, 209], and the oxidation [213]
process that were measured and remeasured by various
researchers. Rate constants that were not available from
the literature were estimated by Denisov’s method
[141]. The mathematical model took into account all
basic elementary stages of the known mechanisms of
polymerization, oxidation, and oxidative polymerization.
At present, the computer simulation experiments
performed by Kurochkin at the Institute of Problems of
Chemical Physics, Russian Academy of Science made
it possible to collect a kinetic data array concerning the
oxidation polymerization that is necessary for the
experimental implementation of the synthesis of HBPs.
EFFECT OF CHEMICAL AND TOPOLOGICAL
STRUCTURES
OF HBPS ON THEIR MACROSCOPIC
PROPERTIES. CHARACTERISTICS OF HBPS
VALUABLE FOR PRACTICE
AND THEIR FORMATION PROCEDURES
The unusual topological structure of the core–shell
type with a very high local concentration of chain ends
in the peripheral layer of macromolecules and with a
high concentration of branching junctions in the core is
responsible for unique macroscopic characteristics of
HBPs, such as solubility and thermodynamic compati-
bility, as well as high sorption ability combined with an
ability to transport sorbates in media in which sorbates
are insoluble. The chemical structure of HBP macro-
molecules that determines the nature of functional
groups in the shell and the length and flexibility of
interjunction chains in the core is a no less significant
factor that controls the formation of macroscopic prop-
erties.
An extremely wide range of practical applications
of HBPs is based on a diverse assortment of HBPs,
since each practical application necessitates that HBPs
exhibited quite specific properties determined by the
chemical and topological structures of hyperbranched
macromolecules. In this connection, highly significant
attention is given the identification of the chemical and
topological structural elements of HBPs that control
one or some of these characteristics. The structure–
property relationship is examined for the series of
HBPs with successively varied structural parameters,
primarily the type of functional groups, the length and
flexibility of interjuinction chains, the number of gen-
erations, and the molecular mass parameters of macro-
molecules. A large body of information has already
been accumulated in this direction that allows one to
make some conclusions useful for precisely tailoring
the properties of HBPs that are necessary for the advan-
tageous application of these polymers in this specific
field.
A great quantity of information of this kind was
reported in the papers by Sherrington, Sato, and Ishizu
et al., who were discussed above in sections devoted to
the synthesis of HBPs. These researchers synthesized
systematic objects, performed their chemical and topo-
logical characterization, and studied their most impor-
tant macroscopic properties. In [142], the effect of the
length of chemically identical interjunction chains on
the distinctive features of HBPs was ascertained and an
important conclusion was drawn; namely, as the length
of chains increases above a certain limiting value, the
unique distinctive features of these polymers disappear
(the matter at hand primarily involves such properties
as high solubility, thermodynamic compatibility, and
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
high sorption ability combined with the ability to trans-
port sorbates in media in which sorbates are insoluble).
For the selected poly(ethylene oxide) structure of inter-
junction chains, the limiting value of chain length was
estimated as ~10 units.
Below, we will consider the most systematic data
[11, 139, 140] of the structure–properties relationship
reported for two families of HBPs produced industri-
ally, namely, the Boltorn family (Perstorp Specialty
Chemicals AB (Sweden) with a division called Perstorp
Polyols Inc. (USA)) and Hybrane (DSM Fine Chemi-
cals, Holland).
The Boltorn HBPs are polyesters synthesized
through the polycondensation of the AB2 monomer—
2,2-dimethylolpropionic acid (A–COOH and B–
OH)—via polyesterification and carrying, accordingly,
hydroxyl groups as end functional groups forming a
shell. The base series under consideration includes
marks H20, H30, and H40 differing in the number of
generations (z = 2, 3, and 4, respectively), the number
of functional groups OH (Φ = 16, 32, and 64), Mw
(2100, 3500, and 5100), polydispersity Mw /Mn (1.3,
1.5, and 1.8), glass transition temperature Tg (31, 38,
42°ë), and melt viscosity η at 110°ë (7, 40, and 100 Pa
s). The total effect of factors z, Φ, Mw, and Mw /Mn man-
ifests itself as an insignificant, though nevertheless sys-
tematic, increase in Tg and as a very strong rise in η
(upon a simultaneous rise in all these factors z, Φ, Mw,
and Mw /Mn). A very pronounced change in Tg, η and in
the solubility of the HBPs of the H series was observed
upon the partial replacement of hydroxyls with other
functional groups. Thus, for example, a partial esterifi-
cation of OH groups in the H20 aliphatic monocarbox-
ylic acid leads to an extremely marked reduction in Tg
and η.
The replacement of hydroxyls in the HBPs of the H
series with long aliphatic chains capable of crystalliza-
tion leads to the appearance of a well-defined tempera-
ture of melting instead of Tg, indicating formation of
the crystalline phase. The melt of the stating H20
behaves as a pseudothixotropic (non-Newtonian) liq-
uid. The thixotropic structure is destroyed only at high
strain rates. Evidently, thixotropy results from strong
intermolecular interactions involving hydrogen bonds
formed by hydroxyls. The replacement of ~50 mol %
hydroxyls with nonpolar aliphatic chains facilitates the
ideally Newtonian behavior. It was shown that as z, A,
and Mw are increased (on passage from H20 to H40),
deviation from Newtonian behavior decreases. It is pos-
sible that the main cause of this phenomenon is that the
conformational capabilities of macromolecular
branches carrying OH groups widen as the length of the
chains increases (and, hence, flexibility increases)
withan increase in z. Because of the accumulation of a
large amount of hydroxyls on the periphery of HBP
macromolecules, an additional possibility of intramo-
lecular realization of hydrogen bonds (instead of inter-
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
347
macromolecular) appears owing to the draw of periph-
eral hydroxyls inside macromolecules.
A partial replacement of hydroxyls in the HBPs of
the H series allows one to vary their characteristics in a
wide range and to meet the requirements of certain
areas of application.
In the case of the HBPs of the Boltorn family, only
the nature of end functional groups was varied but the
framework of macromolecules remained unchanged.
As regards the Hybrane HBPs, the chemical struc-
ture of the framework was also varied. HBPs of this
type are hyperbranched poly(ester amides) synthesized
through the interaction of diisopropanol with cyclohex-
anedicarboxylic anhydride (the base HBP). As in the
case of Boltorn, hydroxyls serve as the end functional
groups that form the shell. The chemical structure of
the repeating unit (interjunction chain) B is as follows:
O O
N O
.
HBPs of the Hybrane family, depending on the
trademark, are characterized by Mn = (1–5) × 103
(broad molecular mass distribution) and are either vis-
cous liquids under standard conditions (T
20°C) or
solid low-melting resins. These HPBs show solubility
in the majority of organic solvents of moderate polarity.
In nonpolar (hydrocarbons) or strongly polar (water)
liquids, these HBPs exhibit solubility only after appro-
priate modification (see below). The polymers are sta-
ble up to 250°ë, are hydrolytically stable at pH 5–9,
and demonstrate well-defined biodegradability. By
varying a set of Φ, chemical structure B, and the value
of Mn, one may significantly affect the following char-
acteristics: solubility, thermodynamic compatibility,
Tg, surface activity (when used as surfactants), and
rheological behavior. The set of Φ is varied via the
esterification of hydroxyls of the base HBP with the use
of the following acids: fatty acids, benzoic, meth-
acrylic, and functionalized acids. If solubility in water
is required, HBPs with functional groups –N(CH3)2 and
–COOH are synthesized. The replacement of hydroxyls
in the base HBP through the esterification with fatty
(lauric) acid sharply reduces the value of Tg. A partial
replacement (~50%) of hydroxyls in the base the HBP
through esterification with stearic acid leads to a cata-
strophic reduction in the viscosity of the melt.
The effect of the chemical structure of B on the
properties of the HBPs of the Hybrane family was stud-
ied by varying the nature of one of the starting compo-
nents during synthesis, namely, acid anhydrides in the
following series: cyclohexanedicarboxylic, siccine,
phthalic anhydrides, and siccine anhydride containing
C12H29 and even more complex substituents.
348 KOROLEV, BUBNOVA
It turned out that the composition of anhydride frag-
ments of the B block has a very strong effect on the sol-
ubility of HBP in water, namely, the successive replace-
ment of cyclohexanedicarboxylic anhydride in the
starting composition with siccine anhydride acid by 20,
40, 60, 80, and 100% successively facilitates the transi-
tion from full insolubility to weak, then strong
swelling, partial, and full solubility, and, finally, to
good solubility.
In addition, it was shown that viscosity in solutions
and compositions may be controlled with a change in
B, since a record low viscosity for 50% solutions of
HBPs was attained. A very low level of η in the case of
HBPs compared to linear analogs (this feature is com-
mon to a greater or lesser extent to all HBPs) opens
much wider possibilities for their practical applica-
tions, especially for the manufacture of varnish-and-
paint compositions and polymer composites.
A change in the nature of end functional groups in
the case of Hybrane polymers led to achievement of
several record parameters; at a certain ratio of hydro-
philic and hydrophobic Φ units in the Hybrane HBPs,
they acquire the properties of very active surfactants.
For example, upon the esterification of a part of the
hydrophilic groups (hydroxyl) in the base HBP with
fatty acid containing the hydrophobic chain ë12 (lau-
ric), it becomes a highly active surfactant.
The activity of surfactants of this type (surface ten-
sion is a measure of this activity) is extremely high,
namely, a two-fold reduction in surface tension is
achieved even at [surfactant]
10–2%. A high effi-
ciency of hyperbranched surfactants in contrast to sur-
factants of other kinds is determined by the following
factors: a very high local concentration of polar and
apolar groups in the volume of a macromolecule, the
possibility of controlling the ratio of these groups in a
macromolecule (in order to attain its optimal balance),
and a low critical micellazation concentration (the
CMC parameter).
The relationship between hydrophilic and hydro-
phobic groups in macromolecules is a factor of para-
mount importance for another property of HBPs, i.e.,
the ability to adsorb on the surface of solids (including
polymers) as extremely high-density films (the ques-
tion is the density of surface coverage). Continuous
coverage of the surface (without defects like bare
microregions), as evidenced by modern methods, is
observed even at a film thickness of 7–10 nm. A similar
filling in the case of linear polymers is achieved only at
a thickness of 10–20 µm, that is, ~1000 times thicker.
Hybrane HBPs have already found use as materials
for electronics and microelectronics, for painting (as
nanocapsules for dye molecules), as polymer materials
for stomatology, chemicals for the textile, paper, and oil
industries, as detergents, and for the manufacture of
personal hygiene products.
Hybrane HBPs also hold promise as adhesives, sup-
ports (substrates) for catalysts, foaming and anitifoam-
ing agents, emulsifiers and deemulsifiers, rheological
additives, dispersing agents, moisturizers, and acceler-
ators of engineering processes.
INTERACTION OF HBPS
WITH POLYMER MATRICES.
HBPs AS MODIFIERS OF GLASSY
AND SEMICRYSTALLINE POLYMER
MATERIALS
The necessity of gaining insight into the interaction
of HBPs with polymer matrices appeared, as is fre-
quently the case of basic scientific problems, owing to
the use of HBP additives as highly efficient modifiers in
polymer material science. Progress has been achieved
in two directions of this application area of HBPs. The
first direction includes the addition of small amounts of
HBPs in engineering polymer materials in order to
improve their mechanical characteristics (primarily to
decrease their brittleness owing to an increase in the
fracture toughness) and to enhance the technological
effectiveness in the manufacture of the materials
(mainly to reduce viscosity of the starting mixture from
which an article is molded). The second direction pro-
vides the use of small amounts of HBPs for designing
functional polymer materials. In this case, hyper-
branched macromolecules are used as nanocapsules
filled with guest molecules of functional compounds
(chromotropes of the spiropyran types, scintillators,
and clusters of Au and other metals, including several
atoms, dyes) and ensuring ideally uniform distribution
of corresponding compounds in the bulk of functional
materials, for example, self-shading organic glasses-
chameleons, irradiation sensors, polymer plasmons,
and colored organic glasses.
In any case (especially when HBPs are used as
nanocapsules), it is necessary to know whether the level
of molecular mobility inside HBPs macromolecules
changes after they appeared to be included into a poly-
mer matrix (glassy or semicrystalline). In other words,
it is necessary to know the character of the interactions
of HBP macromolecules (or their aggregates, if the
aggregation of HBPs is inevitable during formation of
the matrix) with matrices since the efficiency of modi-
fication with HBPs additives depends primarily on
what degree HBP macromolecules keep their auton-
omy. Actually, in the case that the autonomy of hyper-
branched macromolecules or their aggregates is pre-
served, they prove to be capable of forming nanosized
centers in a matrix with the predetermined combination
of properties specified by the chemical and topological
structure of the selected HBP.
Practically all of the voluminous data concerning
the modification of polymer matrices with HBPs pro-
vide indirect evidence that the autonomy is preserved.
There is straightforward evidence for this fact [214,
215] obtained from measurements of glass transition
temperatures of HBPs (Tg1), polyepoxide polymer
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
matrices (Tg2, with Tg2 > Tg1), and polymer matrices
containing small amount of HBPs. It was shown that in
the latter case, two regions of α transition that are well-
defined on the temperature scale are observed (from the
temperature dependence of tan δ estimated from
dynamic mechanical measurements), including a low-
temperature near Tg1 and a high-temperature near Tg2.
With an increase in the concentration of HBP additives,
the intensity of the tan δ peak corresponding to Tg1
increased. Since the values of Tg are determined by the
level of molecular mobility, the results from [214, 215]
lead us to state that HBPs (polyesters with end hydroxyl
groups) preserve their own level of molecular mobility,
that is, they conserve autonomy, in polymer (polyep-
oxide matrices).
For semicrystalline polymer matrices, en extremely
interesting and unusual type of interaction with HBPs is
observed, namely, small additives of HBPs to the melts
of crystallizable polymers (polyolefins and polycarbon-
ates [216–224]) prompted the formation of very small
and nearly equidimensional spherulites in the course of
crystallization instead of large spherulites of different
sizes formed in the absence of HBPs. Accordingly, the
mechanical properties of the matrices improved
sharply. An additional advantage was a marked reduc-
tion in the viscosity of melts. This effect appreciably
facilitated the molding of articles.
The interaction of HBPs with glassy polymer matri-
ces have been studied in detail simultaneously by sev-
eral laboratories from abroad equipped with modern
instruments, largely for polyepoxide matrices. Among
these studies, the most comprehensive data were
reported in [214, 215, 225–233]. The data published
before 2001 were analyzed and surveyed in the review
[234].
An analysis of all of the above-mentioned publica-
tions devoted to the interaction of HBPs with glassy
polymer matrices gives us grounds to the draw the main
following conclusion.
During the formation of a matrix (via polymeriza-
tion in the case of thermoreactive systems or from solu-
tion (melt) in the case of thermoplastics), the HBP addi-
tive may either remain in the dissolved state (if the con-
centration of HBP is small and the thermodynamic
affinity for the matrix polymer is high) or, due to
microphase separation, may partially or fully (depend-
ing on concentration and level of thermodynamic affin-
ity) aggregate as rather small (2–5 µm) monodisperse
spherical particles that are very uniformly distributed
within the matrix. All authors convincingly prove that it
is exactly these particles that are responsible for the
reduction in the brittleness of matrices. Microphase
separation processes are inherent to polymer modifiers
of any type, not only to HBPs, but it is in the case of
HBPs, as follows from electron microscopy data, that
form morphological structures with the most uniform
volume distributions of the disperse phase. Evidently,
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
349
such uniformity, which is the distinguishing feature of
HBP interaction with the matrix, provides an incom-
mensurably higher efficiency of HBP additives as mod-
ifiers compared to other polymer modifiers.
Advantages of HBPs as highly efficient modifiers
manifest themselves most vividly in the case of poly-
mer composites with a high degree of filling with dis-
perse particles or fibers, even more so in the case of
nanocomposites [235–238]. Actually, when highly dis-
perse fillers (mineral particles and carbon microfibrous
dispersions) are used for strengthening of composites),
the main problem is the aggregation of nanofiller parti-
cles, which, on one hand, leads to their undesirable
enlargement (the efficiency of fillers decrease with the
enlargement of particles) and, on the other hand, to the
nonuniform distribution of the polymer matrix of the
composite. Both phenomena (enlargement and nonuni-
formity) confine the strengthening effect. Aggregation
becomes more distinct with an increase in the filler con-
centration. At the stage preceding formation of the
polymer matrix, the aggregation of the filler promotes
an increase in the viscosity of the starting composition,
thus complicating the necessary engineering proce-
dures.
The use of HBPs is an ideal variant for suppression
of aggregation owing to an increased level of thermo-
dynamic compatibility of HBPs and the possibility of a
wide variation in the set of functional groups at the
periphery of macromolecules in order to provide opti-
mal interaction with both the surface of fillers and the
polymer matrix of the composite, with the rheology of
the starting mixture being the best compared to other
polymer additives.
The advantages of HBPs become even more pro-
nounced when they are used in composites, as nano-
sized filler demonstrates incommensurably higher
aggregation ability due to its surface being more devel-
oped.
CONCLUSIONS
The discovery of unique properties of hyper-
branched macromolecules stimulated the rapid devel-
opment of the field during the last decade. Numerous
syntheses of diverse HBPs and procedures for their
identification have been proposed. The topological fea-
tures of HBP macromolecules responsible for their
most important distinctive features have been studied,
namely, a high level of solubility and thermodynamic
compatibility, low viscosity of solutions, aggregation
stability in solutions (including highly concentrated),
and the ability to serve as nanocapsules for compounds
sorbed inside macromolecules. The main topological
feature of HBPs is the high volume concentration of
chain units inside macromolecules because of the
branching without crosslinking that grows with an
increase in the degree of branching and, hence, is very
weak compared to linear polymers the molecular mass
350 KOROLEV, BUBNOVA
dependence of the hydrodynamic volume of macromol-
ecules, as the higher the molecular mass is, the more
compact the molecular packing will be. Such a compact
packing of HBP macromolecules and a large number of
free chain ends containing functional groups at their
periphery are the main structural and physical causes of
the appearance of unique properties of HBPs.
In the field of synthesis of HBPs via step-growth
polymerization (polycondensation) methods, the key
problems have been solved. Diverse variants of synthe-
sis have been developed, including such reliable and
efficient possibilities that the commercial production of
several types of HBPs will be launched in Europe at the
earliest possible date. These are aliphatic polyesters
and poly(ester amides) with varied numbers of branch-
ing cascades and a variable set of end functional groups
(hydroxyl groups in basic types and with different
degrees of replacement of hydroxyls with aliphatic,
epoxy and others groups in modificates).
HBPs have found extremely rapid applications in
various fields of engineering and always with success.
A particularly high efficiency of HBPs was achieved
through their use as modifiers of polymer materials
(engineering, paint-and-vanish, organic glasses, and
polymer nanocomposites), as a polymer basis of mate-
rials useful for electronics, microelectronics, and cur-
rent sources of a new generation (insulators with a
record low dielectric permittivity, polyelectrolytes,
semiconductors, and polymer plasmons), as electroop-
tical materials (including solar batteries), nanocapsules
for functional additives (dyes, phototropic and other
compounds for optical organic glasses), as pharmaco-
logical nanocapsules in medicine, sensors for supersen-
sitive analyzers for chemical and ecological purposes,
and nanosized chemical and biochemical reactors. The
progress achieved owing to the use of HBPs is so high
that it allows one to speak of a revolution in polymer
materials science [239].
Despite the vast array of data accumulated in the
field of HBPs, the following problems remain urgent:
(1) The creation of methods for the chemical design
of HPB macromolecules with the desired topological
architecture aimed at the synthesis of a wide range of
HBPs with the target variation in the degree of branch-
ing, functionality, length, and nature of interjunction
chains. Of special attention is the tendency toward the
synthesis of HBPs via radical (chain) polymerization
processes. As opposed to the step-growth process, the
free-radical polymerization allows a wider variation in
both the topological structure of macromolecules and a
set of functional groups.
(2) A search for simple and well-controllable reac-
tions of addition to the functional groups of HBPs that
have been already produced in industry for their chem-
ical modification. These studies are aimed at a marked
widening of a rather narrow assortment of commercial
HBPs so as to meet the requirements of specific practi-
cal applications.
(3) Elaboration of methods for the identification of
the chemical and topological structure and molecular
parameters of HBP macromolecules.
(4) Establishment of the correlation between the
molecular properties of HBPs (chemical and topologi-
cal structure, molecular parameters, and functionality)
and macroscopic characteristics (thermodynamic com-
patibility, sorption ability, and resistance against asso-
ciative interaction).
(5) Study of the interaction of HBP macromolecules
with glassy (polyester, polyepoxide, and polymethacry-
late) and semicrystalline (polyolefins and polyamide)
polymer matrices. The solution of this problem is a pre-
requisite for the development of a scientific basis for
the modification of engineering polymer materials with
HBP additives.
REFERENCES
1. P. J. Flory, J. Am. Chem. Soc. 74, 2718 (1952).
2. F. Aulenta, W. Hayes, and S. Rannard, Eur. Polym. J.
39, 1741 (2003).
3. M. N. Bochkarev and M. A. Katkova, Usp. Khim. 64,
1106 (1995).
4. Yu. D. Semchikov, Sorosovskii Obrazovatel’nyi Zh.,
No. 12, 45 (1998).
5. C. Gao and D. Yan, Prog. Polym. Sci. 29, 183 (2004).
6. G. V. Korolev and A. P. Marchenko, Usp. Khim. 69, 447
(2000).
7. B. R. Smirnov, A. P. Marchenko, G. V. Korolev, et al.,
Polymer Science, Ser. A 41, (1999) [Vysokomol. Soe-
din., Ser. A 41, 1974 (1999)].
8. T. Sato, Y. Arima, M. Seno, and T. Hirano, Macromole-
cules 38, 1627 (2005).
9. J. D. Campbell, F. Teymour, and M. Morbidelli, Macro-
molecules 38, 752 (2005).
10. G. V. Korolev, T. F. Irzhak, and V. I. Irzhak, Khim. Fiz.
21, 58 (2002).
11. Properties and Applications of Boltorn, Dendritic Poly-
mers, Ed. by B. Pettersson (Perstorp Speciality Chemi-
cals AB, 2001).
12. G. A. Razuvaev, L. S. Boguslavskaya, and R. A. Bara-
bashina, Zh. Org. Khim. 8, 1601 (1972).
13. M. N. Bochkarev, V. B. Silkin, L. P. Maiorova, et al.,
Metalloorg. Khim. 1, 196 (1988).
14. M. N. Bochkarev, Proc. Indian Acad. Sci., Sect. A 55,
170 (1989).
15. M. N. Bochkarev, Yu. D. Semchikov, V. B. Silkin, et al.,
Vysokomol. Soedin., Ser. B 31, 643 (1989).
16. Yu. D. Semchikov, S. D. Zaitsev, M. A. Katkova, et al.,
Polymer Science, Ser. A 43, 900 (2001) [Vysokomol.
Soedin., Ser. A 43, 1464 (2001)].
17. O. G. Zakharova, S. D. Zaitsev, Yu. D. Semchikov, et al.,
Polymer Science, Ser. A 47, 901 (2005) [Vysokomol.
Soedin., Ser. A 47, 1573 (2005)].
18. M. N. Bochkarev, I. I. Brezhneva, M. A. Katkova, et al.,
Polymer Science, Ser. A 44, 89 (2002) [Vysokomol.
Soedin., Ser. A 44, 104 (2002)].
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
19. B. V. Lebedev, N. N. Smirnova, L. Ya. Tsvetkova, et al.,
Polymer Science, Ser. A 46, 526 (2004) [Vysokomol.
Soedin., Ser. A 46, 849 (2004)].
20. S. D. Zaitsev, A. A. Turshatov, G. M. Pavlov, et al.,
Polymer Science, Ser. B 46, 241 (2004) [Vysokomol.
Soedin., Ser. B 46, 1443 (2004)].
21. I. I. Pestova, E. N. Khanov, T. I. Kulikova, et al., Poly-
mer Science, Ser. B 46, 237 (2004) [Vysokomol. Soe-
din., Ser. B 46, 1438 (2004)].
22. A. M. Muzafarov, E. A. Rebrov, and V. S. Papkov, Usp.
Khim. 60, 1596 (1991).
23. V. V. Kazakova, V. D. Myakushev, T. V. Strelkova, and
A. M. Muzafarov, Polymer Science, Ser. A 41, 283
(1999) [Vysokomol. Soedin., Ser. A 41, 423 (1999)].
24. M. V. Ryabkov, T. A. Bykova, B. V. Lebedev, et al.,
Polymer Science, Ser. A 42, 1012 (2000) [Vysokomol.
Soedin., Ser. A 42, 1531 (2000)].
25. C. Drohmann, M. Möller, O. B. Gorbatsevich, and
A. M. Muzafarov, J. Polym. Sci., Part A: Polym. Chem.
38, 741 (2000).
26. A. N. Ozerin, A. M. Muzafarov, V. I. Gordeliy, et al.,
Macromol. Symp. 195, 171 (2003).
27. A. V. Bystrova, E. A. Tatarinova, M. I. Buzin, and
A. M. Muzafarov, Polymer Science, Ser. A 47, 820
(2005) [Vysokomol. Soedin., Ser. A 47, 1452 (2005)].
28. E. B. Tarabukina, A. A. Shpyrkov, D. V. Potapova, et al.,
Polymer Science, Ser. A 47, 1304 (2005) [Vysokomol.
Soedin., Ser. A 47, 2157 (2005)].
29. P. V. Buzin, M. Yu. Yablokova, A. A. Kuznetsov, et al.,
in Structure and Dynamics of Molecular Systems (Mari-
isk. Gos. Univ., Ioshkar-Ola, 2003), No. X, Part 1, p. 24.
30. A. A. Kuznetsov, P. V. Buzin, and M. Yu. Yablokov, in
Structure and Dynamics of Molecular Systems (Mari-
isk. Gos. Univ., Ioshkar-Ola, 2004), No. XI, Part 1,
p. 46.
31. A. Kuznetsov, A. Tsegelskaya, V. Kaminsky, et al., CD-
ROM, Extended Abstracts of European Polymer Con-
gress, Moscow, 2005, P1.2-28, Ref. 6134.
32. A. Kuznetsov, A. Tsegelskaya, and V. Kaminsky, CD-
ROM, Extended Abstracts of European Polymer Con-
gress, Moscow, 2005, P7.4-15, Ref. 6125.
33. A. Yu. Bilibin, G. G. Egorova, N. V. Girbasova, et al.,
Polymer Science, Ser. A 46, 89 (2004) [Vysokomol.
Soedin., Ser. A 46, 197 (2004)].
34. N. V. Girbasova, I. I. Migunova, I. R. Raspopova, and
A. Yu. Bilibin, Polymer Science, Ser. A 45, 320 (2003)
[Vysokomol. Soedin., Ser. A 45, 550 (2003)].
35. G. V. Korolev, T. F. Irzhak, and V. I. Irzhak, Polymer
Science, Ser. A 44, 1 (2002) [Vysokomol. Soedin., Ser.
A 44, 5 (2002)].
36. G. V. Korolev, T. F. Irzhak, and V. I. Irzhak, Polymer
Science, Ser. A 43, 594 (2001) [Vysokomol. Soedin.,
Ser. A 43, 970 (2001)].
37. G. V. Korolev, V. I. Irzhak, and T. F. Irzhak, Polymer
Science, Ser. A 43, 1236 (2001) [Vysokomol. Soedin.,
Ser. A 43, 2106 (2001)].
38. G. V. Korolev, T. F. Irzhak, and V. I. Irzhak, Macromol.
Symp. 171, 11 (2001).
39. V. I. Irzhak, Usp. Khim. 73, 275 (2004).
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
351
40. M. A. Krykin, A. M. Vasserman, M. V. Motyakin, et al.,
Polymer Science, Ser. A 44, 836 (2002) [Vysokomol.
Soedin., Ser. A 44, 1325 (2002)].
41. M. A. Fadeev, A. V. Rebrov, L. A. Ozerina, et al., Poly-
mer Science, Ser. A 41, 189 (1999) [Vysokomol. Soe-
din., Ser. A 41, 290 (1999)].
42. V. I. Selikhova, V. M. Neverov, E. A. Sinevich, et al.,
Polymer Science, Ser. A 47, 103 (2005) [Vysokomol.
Soedin., Ser. A 47, 228 (2005)].
43. G. P. Vlasov, I. I. Tarasenko, S. V. Valueva, et al., Poly-
mer Science, Ser. A 47, 422 (2005) [Vysokomol. Soe-
din., Ser. A 47, 731 (2005)].
44. S. V. Lyulin, A. V. Lyulin, and A. A. Darinskii, Polymer
Science, Ser. A 46, 189 (2004) [Vysokomol. Soedin.,
Ser. A 46, 321 (2004)].
45. Y. H. Kim and O. W. Webster, Polym. Prepr. (Am.
Chem. Soc., Div. Polym. Chem.) 29, 310 (1988).
46. Y. H. Kim and O. W. Webster, J. Am. Chem. Soc. 112,
4592 (1990).
47. Y. H. Kim and O. W. Webster, Macromolecules 25,
5561 (1992).
48. Y. H. Kim and R. Beckerbauer, Macromolecules 27,
1968 (1994).
49. K. E. Uhrich, C. Hawker, J. M. J. Frechet, and S. R. Turner,
Macromolecules 25, 4583 (1992).
50. T. M. Miller, T. X. Neenan, E. W. Kwock, and S. M. Stein,
J. Am. Chem. Soc. 115, 356 (1993).
51. V. Percec and M. Kawasumi, Macromolecules 25, 3843
(1992).
52. V. Percec, P. Chu, and M. Kawasumi, Macromolecules
27, 4441 (1994).
53. C. J. Hawker, R. Lee, and J. M. J. Fréchet, J. Am. Chem.
Soc. 113, 4583 (1991).
54. P. Kambouris and C. J. Hawker, J. Chem. Soc., Perkin
Trans. 1, 2717 (1993).
55. K. L. Wooley, C. J. Hawker, R. Lee, and J. M. J. Frechet,
Polym. J. (Tokyo) 26, 187 (1994).
56. K. L. Wooley, J. M. J. Frechet, and C. J. Hawker, Poly-
mer 35, 4489 (1994).
57. S. R. Turner, B. Voit, and F. Walter, Polym. Mater. Sci.
Eng. 68, 57 (1993).
58. S. R. Turner, B. Voit, and T. H. Mourey, Macromole-
cules 26, 4617 (1993).
59. S. R. Turner and B. Voit, Polym. Prepr. (Am. Chem.
Soc., Div. Polym. Chem.) 34, 79 (1993).
60. S. R. Turner, Polym. Mater. Sci. Eng. 74, 437 (1996).
61. S. R. Turner and B. Voit, Polym. Prepr. (Am. Chem.
Soc., Div. Polym. Chem.) 33, 184 (1992).
62. S. R. Turner, F. Walter, B. Voit, and T. H. Mourey, Mac-
romolecules 27, 1611 (1994).
63. E. Malmström, M. Johansson, and A. Hult, Polym.
News 22, 128 (1997).
64. M. Johansson, E. Malmström, and A. Hult, J. Polym.
Sci., Part A: Polym. Chem. 31, 619 (1993).
65. H. Andersson, U. W. Gedde, and A. Hult, Macromole-
cules 29, 1649 (1996).
66. E. Malmström, F. Liu, R. Boyd, et al., Polym. Bull.
(Berlin) 32, 679 (1994).
67. E. Malmström, M. Johansson, and A. Hult, Macromol-
ecules 28, 1698 (1995).
352 KOROLEV, BUBNOVA
68. E. Malmström and A. Hult, Macromolecules 29, 1222
(1996).
69. E. Malmström and A. Hult, Polym. Mater. Sci. Eng. 73,
349 (1995).
70. H. Magnusson, E. Malmström, and A. Hult, Macromol-
ecules 33, 3099 (2000).
71. M. Trolsas, J. Hedrick, O. Mecerreyes, et al., J. Polym.
Sci., Part A: Polym. Chem. 36, 3187 (1998).
72. H. R. Kricheldorf, O. Stoeber, and D. Luebbers, Macro-
molecules 28, 2118 (1995).
73. H. R. Kricheldorf, G. Loehden, and O. Stoeber, Polym.
Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 36, 749
(1995).
74. H. R. Kricheldorf and T. Stukenbrock, J. Polym. Sci.,
Part A: Polym. Chem. 36, 2347 (1998).
75. M. Trollsas and J. L. Hedrick, Macromolecules 31,
4390 (1998).
76. K. E. Uhrich, S. Boegeman, J. M. J. Fréchet, and
S. R. Turner, Polym. Bull. (Berlin) 25, 551 (1991).
77. H. R. Kricheldorf and O. Bolender, J. Macromol. Sci.,
Pure Appl. Chem. 35, 903 (1998).
78. Y. H. Kim, J. Am. Chem. Soc. 114, 4947 (1992).
79. G. Yang, M. Jikei, and M. Kakimoto, Macromolecules
32, 2215 (1999).
80. G. Yang, M. Jikei, and M. Kakimoto, Macromolecules
31, 5964 (1998).
81. Y. Ishida, A. C. F. Sun, M. Jikei, and M. Kakimoto,
Macromolecules 33, 2832 (2000).
82. L. J. Hobson, A. M. Kenwright, and W. J. Feast, Chem.
Commun., No. 19, 1877 (1997).
83. L. J. Hobson and W. J. Feast, Polymer 40, 1279 (1999).
84. D. H. Bolton and K. L. Wooley, Macromolecules 30,
1890 (1997).
85. C. J. Hawker and F. Chu, Macromolecules 29, 4370
(1996).
86. A. Morikawa, Macromolecules 31, 5999 (1998).
87. C. F. Shu, C. M. Leu, and F. Y. Huang, Polymer 40, 6591
(1999).
88. C. F. Shu and C. M. Leu, Macromolecules 32, 100
(1999).
89. R. Spindler and J. M. J. Fréchet, Macromolecules 26,
4809 (1993).
90. A. Kumar and S. A. Ramakrishnan, J. Chem. Soc.,
Chem. Commun., No. 18, 1453 (1993).
91. A. Kumar and S. A. Ramakrishnan, J. Polym. Sci.,
Part A: Polym. Chem. 34, 839 (1996).
92. R. M. Versteegen, R. P. Sijbesma, and E. W. Meijer,
Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.)
40, 839 (1999).
93. J. Karger-Kocsis, J. Frohlich, O. Gryshchuk, et al.,
Polymer 45, 1185 (2004).
94. O. Gryshchuk, N. Jost, and J. Karger-Kocsis, Polymer
43, 4763 (2002).
95. T. M. Londergan, Y. You, M. E. Thompson, and W. P.
Weber, Macromolecules 31, 2784 (1998).
96. P. Lu, J. K. Paulasaari, and W. P. Weber, Macromole-
cules 29, 8583 (1996).
97. L. J. Mathias and T. W. Carothers, J. Am. Chem. Soc.
113, 4043 (1991).
98. A. Muzafarov, M. Golly, and M. Möller, Macromole-
cules 28, 8444 (1995).
99. K. Yoon and D. Y. Son, Macromolecules 32, 5210
(1999).
100. C. Lach and H. Frey, Macromolecules 31, 2381 (1998).
101. C. Gao and D. Y. Yan, Chem. Commun., No. 1, 107
(2001).
102. C. Gao, Y. M. Xu, H. Zhang, and D. Y. Yan, Polym.
Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 44, 845
(2003).
103. C. Gao, Y. M. Xu, D. Y. Yan, and W. Chen, Biomacro-
molecules 4, 704 (2003).
104. C. Gao and D. Yan, Macromolecules 36, 613 (2003).
105. D. Yan and C. Gao, Macromolecules 33, 7693 (2000).
106. D. Y. Yan, C. Gao, W. Tang, et al., in Proceedings of
CCS Congress, China, 2000, p. 573.
107. C. Gao and D. Y. Yan, Chem. World (Suppl.) 42, 229
(2001).
108. C. Gao, D. Y. Yan, X. Y. Zhu, and W. Huang, Polymer
42, 7603 (2001).
109. C. Gao, D. Y. Yan, and W. Tang, Macromol. Chem.
Phys. 202, 2623 (2001).
110. C. Gao and D. Y. Yan, Gaodeng Xuexiao Huaxue Xue-
bao 23, 2202 (2002).
111. China Patent No. 02,111,579.6 (2002).
112. H. G. Kou and W. F. Shi, Gaofenzi Xuebao, No. 5554
(2000).
113. China Patent No. 02,111,578.8 (2002).
114. D. M. Muscat, H. Henderickx, G. Kwakkenbos, et al., J.
Am. Soc. Mass Spectrom. 11, 218 (2000).
115. China Patent No. 02,145,100.1 (2002).
116. C. Gao, W. Tang, and D. Y. Yan, J. Polym. Sci., Part A:
Polym. Chem. 40, 2340 (2002).
117. China Patent No. 02,145,097.8 (2002).
118. K. C. Wang, C. Gao, W. Huang, and D. Y. Yan, Polym.
Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 44, 583
(2003).
119. S. Koster, C. G. De Koster, R. A. T. M. van Benthem,
et al., Int. J. Mass Spectrom. 210, 591 (2001).
120. K. C. Wang, C. Gao, W. Huang, and D. Y. Yan, Polym.
Prepr. (Am. Chem. Soc., Div. Polym. Chem.) 44, 888
(2003).
121. C. Gao and D. Y. Yan, Macromolecules 34, 156 (2001).
122. C. Gao, W. Tang, D. Y. Yan, et al., Polymer 42, 3437
(2001).
123. C. Gao, D. Y. Yan, and W. Tang, Macromol. Chem.
Phys. 202, 3035 (2001).
124. C. Gao, W. Tang, D. Y. Yan, et al., Sci. China 44, 207
(2001).
125. P. J. Flory, J. Am. Chem. Soc. 63, 3091 (1941).
126. P. J. Flory, J. Am. Chem. Soc. 63, 3096 (1941).
127. C. Walling, J. Am. Chem. Soc. 67, 441 (1945).
128. P. J. Flory, J. Am. Chem. Soc. 69, 30 (1947).
129. M. Jikei, S. H. Chon, M. Kakimoto, et al., Macromole-
cules 32, 2061 (1999).
130. T. Emrick, H. T. Chang, and J. M. J. Fréchet, Macro-
molecules 32, 6380 (1999).
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
 SYNTHESIS, PROPERTIES, AND PRACTICAL APPLICATION
131. T. Emrick, H. T. Chang, and J. M. J. Fréchet, J. Polym.
Sci., Part A: Polym. Chem. 38, 4850 (2000).
132. L. M. Dai, B. Winkler, L. M. Dong, et al., Adv. Mater.
(Weinheim, Fed. Repub. Ger.) 13, 915 (2001).
133. L. Dai, S. Huang, J. Lu, et al., Polym. Prepr. (Am.
Chem. Soc., Div. Polym. Chem.) 39, 171 (1998).
134. T. Lin, Q. He, F. Bai, and L. Dai, Thin Solid Films 363,
122 (2000).
135. S. Tanaka, K. Takeuchi, M. Asai, et al., Synth. Met. 119,
139 (2001).
136. J. H. Fang, H. Kita, and K. Okamoto, Macromolecules
33, 4639 (2000).
137. H. Chen and J. Yin, J. Polym. Sci., Part A: Polym.
Chem. 40, 3804 (2002).
138. J. Hao, M. Jikei, and M. Kakimoto, Macromolecules
35, 5372 (2002).
139. P. E. Froehling, J. Polym. Sci., Part A: Polym. Chem.
42, 3110 (2004).
140. D. Muscat and R. A. T. M. van Benthem, Top. Curr.
Chem. 212, 41 (2001).
141. E. T. Denisov and T. G. Denisova, in Hahdbook of Free-
Radical Initiators (Wiley, New Jersey, 2003).
142. G. C. Behera and S. Ramakrishnan, Macromolecules
37, 9814 (2004).
143. T. Sato, N. Sato, M. Seno, and T. Hirano, J. Polym. Sci.,
Part A: Polym. Chem. 41, 3038 (2003).
144. T. Sato, M. Hashimoto, M. Seno, and T. Hirano, Eur.
Polym. J. 40, 273 (2004).
145. T. Sato, N. Higashida, T. Hirano, and M. Seno, J.
Polym. Sci., Part A: Polym. Chem. 42, 1609 (2004).
146. T. Sato, Y. Arima, M. Seno, and T. Hirano, Polym. Int.
53, 1138 (2004).
147. T. Sato, H. Ihara, T. Hirano, and M. Seno, Polymer 45,
7491 (2004).
148. T. Sato, T. Miyagi, T. Hirano, and M. Seno, Polym. Int.
53, 1503 (2004).
149. N. O’Brien, A. McKee, D. C. Sherrington, et al., Poly-
mer 41, 6027 (2000).
150. P. A. Costello, I. K. Martin, A. T. Slark, et al., Polymer
43, 245 (2002).
151. A. T. Slark, D. C. Sherrington, A. Titterton, and I. K. Mar-
tin, J. Mater. Chem. 13, 2711 (2003).
152. F. Isaure, P. A. G. Cormack, and D. C. Sherrington, J.
Mater. Chem. 13, 2701 (2003).
153. F. Isaure, P. A. G. Cormack, and D. C. Sherrington,
Macromolecules 37, 2096 (2004).
154. B. R. Smirnov, A. P. Marchenko, G. V. Korolev, et al.,
Vysokomol. Soedin., Ser. A 23, 1042 (1981).
155. B. R. Smirnov, in Porphyrins: Spectroscopy, Electro-
chemistry, Application, Ed. by N. S. Enikolopyan
(Nauka, Moscow, 1987), p. 290.
156. A. Gridnev and S. Ittel, Chem. Rev. 101, 3611 (2001).
157. R. Baudry and D. C. Sherrington, Macromolecules 39,
1455 (2006).
158. A. Hui and A. E. Hamielec, J. Appl. Polym. Sci. 22, 749
(1972).
159. A. Hussain and A. E. Hamielec, J. Appl. Polym. Sci. 22,
1207 (1972).
POLYMER SCIENCE Series C Vol. 49 No. 4 2007
353
160. A. E. Hamielec, J. F. MacGregor, S. Webb, and T. Spychaj,
in Polymer Reaction Engineering, Ed. by K. H. Reichert
and W. Geisler (Hüthig and Wepf, New York, 1986),
p. 185.
161. T. Spychaj and A. E. Hamielec, J. Appl. Polym. Sci. 42,
2111 (1991).
162. J. D. Campbell, F. Teymour, and M. Morbidelli, Macro-
molecules 38, 752 (2005).
163. J. D. Campbell, J. A. Allaway, F. Teymour, and M. Mor-
bidelli, J. Appl. Polym. Sci. 94, 890 (2004).
164. J. P. Fisher and W. Luders, Makromol. Chem. 155, 239
(1972).
165. G. F. Meijs, E. Rizzardo, and S. H. Thang, Macromole-
cules 21, 3122 (1988).
166. G. F. Meijs and E. Rizzardo, Makromol. Chem. 191,
1545 (1990).
167. G. F. Meijs, T. C. Morton, E. Rizzardo, and S. H. Thang,
Macromolecules 24, 3689 (1991).
168. J. D. Campbell and F. Teymour, US Patent No. 5986020
(1999).
169. J. D. Campbell and F. Teymour, US Patent No. 6265511
(2001).
170. Z. Guan, US Patent No. 576711 (1998).
171. C. J. Hawker, J. M. J. Fréchet, R. B. Grubbs, and J. Dao,
J. Am. Chem. Soc. 117, 10763 (1995).
172. M. W. Weimer, J. M. J. Fréchet, and I. Gitsov, J. Polym.
Sci., Part A: Polym. Chem. 36, 955 (1998).
173. S. G. Gaynor, S. Edelman, and K. Matyjaszewski, Mac-
romolecules 29, 1079 (1996).
174. B. Voit, J. Polym. Sci., Part A: Polym. Chem. 38, 2505
(2000).
175. K. Matyjaszewski, S. G. Gaynor, and A. H. E. Müller,
Macromolecules 30, 7034 (1997).
176. G. Cheng, P. F. W. Simon, M. Hartenstein, and
A. H. E. Müller, Macromol. Rapid Commun. 21, 846
(2000).
177. K. Matyjaszewski, S. G. Gaynor, A. Kulfan, and
M. Podwika, Macromolecules 30, 5192 (1997).
178. S. H. Yoo, T. H. Yooh, and J. Y. Jho, Macromol. Rapid
Commun. 22, 1319 (2001).
179. S. H. Yoo, J. H. Lee, J.-C. Lee, and J. Y. Jho, Macromol-
ecules 35, 1146 (2002).
180. J. Bibiao, Y. Yang, J. Xiang, et al., Eur. Polym. J. 37,
1975 (2001).
181. J. Bibiao, Y. Yang, D. Jian, et al., J. Appl. Polym. Sci. 83,
2114 (2002).
182. C. Y. Hong and C. Y. Pan, Polymer 42, 9385 (2001).
183. K. Matyjaszewski and S. G. Gaynor, Macromolecules
30, 7042 (1997).
184. K. Matyjaszewski, J. Pyun, and S. G. Gaynor, Macro-
mol. Rapid Commun. 19, 665 (1998).
185. C. H. Hong, C. Y. Pan, Y. Huang, and Z. D. Xu, Polymer
42, 6733 (2001).
186. T. Otsu, M. Yoshida, and A. Kuriyama, Polym. Bull.
(Berlin) 7, 45 (1982).
187. T. Otsu, A. Kuriyama, and M. Yoshida, Kobunshi Ron-
bunshu 40, 583 (1983).
188. T. Otsu and A. Kuriyama, Polym. Bull. (Berlin) 11, 135
(1984).
354 KOROLEV, BUBNOVA
189. T. Otsu and A. Matsumoto, Adv. Polym. Sci. 136, 75
(1998).
190. T. Otsu, J. Polym. Sci., Part A: Polym. Chem. 38, 2121
(2000).
191. K. Ishizu, K. Tsubaki, A. Mori, and S. Ushida, Prog.
Polym. Sci. 28, 27 (2003).
192. K. Ishizu and Y. Ohta, J. Mater. Sci. Lett. 22, 647
(2003).
193. K. Ishizu, T. Kojima, Y. Ohta, and T. Shibuya, J. Colloid
Interface Sci. 272, 76 (2004).
194. K. Ishizu, T. Shibuya, J. Park, and S. Uchida, Polym.
Int. 53, 259 (2004).
195. K. Ishizu, T. Shibuya, and S. Kawauchi, Macromole-
cules 36, 3505 (2003).
196. K. Ishizu, J. Park, Y. Ohta, and T. Shibuya, J. Appl.
Polym. Sci. 89, 2490 (2003).
197. K. Ishizu, C. Takashimizu, T. Shibuya, and S. Uchida,
Polym. Int. 52, 1010 (2003).
198. K. Ishizu, R. A. Khan, Y. Ohta, and M. Furo, J. Polym.
Sci., Part A: Polym. Chem. 42, 76 (2004).
199. K. Ishizu, A. Mori, and T. Shibuya, Polymer 42, 7911
(2001).
200. K. Ishizu, A. Mori, and T. Shibuya, Des. Monom.
Polym. 5, 1 (2002).
201. K. Ishizu and A. Mori, Polym. Int. 50, 906 (2001).
202. K. Ishizu and A. Mori, Macromol. Rapid Commun. 21,
665 (2000).
203. K. Ishizu, Y. Ohta, and S. Kawauchi, Macromolecules
35, 3781 (2002).
204. K. Ishizu, T. Shibuya, and A. Mori, Polym. Int. 51, 424
(2002).
205. M. M. Mogilevich and E. M. Pliss, Oxidation and Oxi-
dative Polymerization of Unsaturated Compounds
(Khimiya, Moscow, 1990) [in Russian].
206. N. A. Sukhanova, Candidate’s Dissertation in Chemis-
try (Ivanovo, 1971).
207. M. M. Mogilevich, N. A. Sukhanova, O. P. Yablonskii,
and G. V. Korolev, Izv. Vyssh. Uchebn. Zaved., Khim.
Khim. Tekhnol. 16 (12), 1898 (1973).
208. M. M. Mogilevich, N. A. Sukhanova, and G. V. Korolev,
Vysokomol. Soedin., Ser. A 15, 1478 (1973).
209. M. M. Mogilevich, Oxidative Polymerization in Film
Formation Processes (Khimiya, Leningrad, 1977) [in
Russian].
210. C. H. Bamford, W. G. Barb, A. D. Jenkins, and
P. F. Onyon, The Kinetics of Vinyl Polymerization by
Radical Mechanisms (Butterworths, London, 1958;
Inostrannaya Literatura, Moscow, 1961).
211. Ch. Walling, Free Radicals in Solution (Wiley, New
York, 1957; Inostrannaya Literatura, Moscow, 1971).
212. Kh. S. Bagdasar’yan, The Theory of Radical Polymer-
ization (Nauka, Moscow, 1966) [in Russian].
213. E. T. Denisov, Rate Constants of Homolytic Liquid-
Phase Reactions (Nauka, Moscow, 1971) [in Russian].
214. D. Ratna, R. Varley, R. K. Singh Raman, and
G. P. Simon, J. Mater. Sci. 38, 147 (2003).
215. D. Ratna and G. P. Simon, Polymer 42, 8833 (2001).
216. G. Xu, W. F. Shi, M. Gong, et al., Eur. Polym. J. 40, 483
(2004).
217. D. Muscat and R. A. T. M. van Benthem, Top. Curr.
Chem. 212, 41 (2001).
218. G. Jannerfeldt, R. Tornqvist, N. Rambert, et al., Appl.
Compos. Mater. 8, 327 (2001).
219. D. E. Bergbreiter, D. Boren, and A. M. Kippenberger,
Macromolecules 37, 8686 (2004).
220. Z. W. Fu, L. M. Tang, B. H. Guo, and D. S. Liu,
Gaofenzi Xuebao, No. 5, 754 (2003).
221. N. Xu, J. H. Zou, W. F. Shi, et al., Polym. Adv. Technol.
16, 378 (2005).
222. L. M. Tang, T. Qiu, X. L. Tuo, et al., Polym. J. (Tokyo)
34, 112 (2002).
223. X. L. Zhang, L. M. Tang, T. Qiu, et al., Gaodeng Xuex-
iao Huaxue Xuebao 22, 1761 (2001).
224. D. E. Berbreiter, J. G. Franchina, and K. Kabza, Macro-
molecules 32, 4993 (1999).
225. D. Ratna, R. J. Varley, and G. P. Simon, J. Appl. Polym.
Sci. 89, 2339 (2003).
226. R. Mezzenga and J. A. E. Manson, J. Mater. Sci. 36,
4883 (2001).
227. G. Cicala, A. Recca, and C. Restuccia, Polym. Eng. Sci.
45, 225 (2005).
228. R. J. Varley, Polym. Int. 53, 78 (2004).
229. J. Frohlich, H. Kautz, R. Thomann, et al., Polymer 45,
2155 (2004).
230. R. J. Varley and W. Tian, Polym. Int. 53, 69 (2004).
231. M. Sangermano, G. Malucelli, R. Bongiovanni, et al.,
Polym. Int. 54, 917 (2005).
232. M. Sangermano, A. Priola, G. Malucelli, et al., Macro-
mol. Mater. Eng. 289, 442 (2004).
233. M. Sangermano, G. Malucelli, R. Bongiovanni, et al.,
Macromol. Mater. Eng. 289, 722 (2004).
234. R. Mezzenga, L. Boogh, and J. A. E. Månson, Compos.
Sci. Technol. 61, 787 (2001).
235. D. Ratna, O. Becker, R. Krishnamurthy, et al., Polymer
44, 7449 (2003).
236. M. Rodlert, C. J. G. Plummer, Y. Leterrier, et al., J.
Rheol. (N. Y.) 48, 1049 (2004).
237. M. Rodlert, C. J. G. Plummer, L. Garamszegi, et al.,
Polymer 45, 949 (2004).
238. C. J. G. Plummer, L. Garamszegi, Y. Leterrier, et al.,
Chem. Mater. 14, 486 (2002).
239. G. V. Korolev and M. L. Bubnova, Hyperbranched
Polymers as a New Powerful Stimulus for Development
of Three-Dimensional Polymerization and a Revolution
in Polymer Materials Science (Inst. Probl. Khim. Fiz.,
Ross. Akad. Nauk, Chernogolovka, 2006) [in Russian].
POLYMER SCIENCE Series C Vol. 49 No. 4 2007