Three-Dimensional Free-Radical Polymerization, Nanotechnologia, nanotechnologia, materiały i chemia ...

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Three-Dimensional Free-Radical Polymerization
Gennady V. Korolev
·
Michael M. Mogilevich
Three-Dimensional Free-Radical
Polymerization
Cross-Linked and Hyper-Branched Polymers
123
Prof. Dr. Michael M. Mogilevich
Kaznacheyskaya ulitca
Dom 13, flat 1
St. Petersburg 198031
Russia
mmmogilevich@mail.ru
Prof. Dr. Gennady V. Korolev
†
Russian edition:
G.V. Korolev, M.M. Mogilevich: Trekhmernaya radicalnaya polimerizatchiya.
Setchatyae i giperrazvetvlennyae polimerya (2006)
published by “KhimIzdat Publishing House”, St. Petersburg
ISBN 5-93808-121-1
ISBN: 978-3-540-87566-6
e-ISBN: 978-3-540-87567-3
DOI 10.1007/978-3-540-87567-3
Library of Congress Control Number: 2008939224
c
Springer-Verlag Berlin Heidelberg 2009
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Preface
At present, three-dimensional free-radical polymerization (TFRP) is a special field
of radical polymerization. TFRP is characterized by specific kinetic regularities and
mechanisms of processes for the formation of cross-linked or hyper-branched poly-
mers, and they are different from the kinetics and mechanism of classical radical
polymerization.
The fundamental studies of kinetics and mechanism of TFRP with formation of
cross-linked polymers have been carried out in three stages. The first stage lasted
from 1960 until 1983, and the main mechanisms of TFRP of oligo(acrylates) were
established during this stage [1–3]. Condensation telomerization, being a universal
oligo(acrylate) synthesis procedure, allows us to vary certain molecular parameters,
such as length and flexibility of oligomeric blocks, number and type of reactive
groups (methacrylic or acrylic groups), and chemical nature of atomic groups of an
oligomeric block, which represent the centers of strong intermolecular interactions.
For this reason, oligo(acrylates) were very convenient compounds for establish-
ing the main kinetic regularities of TFRP and regularities of formation of polymer
three-dimensional cross-linked structures, according to the so-called microheteroge-
neous mechanism (G.V. Korolev, 1977), at the topological and morphological levels.
During the second stage, which lasted from 1983 until 1995, the kinetic regularities
of TFRP were studied in depth, and additional evidentiary data in favor of the micro-
heterogeneous mechanism of TFRP were found [4, 5]. The last, or third stage (from
1995 until 2005) involved exploration of TFRP under the “living” chains condi-
tions and identification of new regularities associated with the implementation of
these conditions [6], as well as the creation of the new gelation theory applicable to
TFRP, investigation into physical and mechanical properties of cross-linked copoly-
mers, and the interpretation of these properties within the framework of the physical
network model [6].
The technical value of TFRP is generally known. Industrial use of oligo
(acrylates), oligo(estermaleates) in styrene compositions, and oligo-esters modified
by fatty acids of vegetable oils (alkyds) is based on TFRP with cross-linked poly-
mer formation. The interest in TFRP throughout the world has markedly increased
in the 1990s: by 2000 the number of publications on TFRP had grown tenfold. This
growth is explained by the development needs of microelectronics, fiberoptics, and
data storage and transmission devices. TFRP makes polymers highly attractive for
v
vi
Preface
applications related to high-tech materials. The radical chain nature of TFRP en-
ables performing curing of fluid polyunsaturated methacrylates in superfast time
(seconds!) and an easily controlled mode at normal temperature.
It was found, in the middle of the 1990s, that in addition to cross-linked poly-
mers TFRP can also lead to the formation of hyper-branched polymers (HBP)
(non-cross-linked) that have a unique chemical structure and properties which are
different from the structure and properties of all known linear and cross-linked poly-
mers. Polymer chains of HBP diverge outward symmetrically in three-dimensional
space from the point or linear center of symmetry and look like a branching tree. The
unique properties of HBP turned out to be so popular that during the next decade
these polymers found use in various applications for polymer materials from micro-
electronics to medicine. They caused a revolution in polymer materials technology.
And, all this gave a new powerful impulse to the development of the entire TFRP
field—the intensive and successful investigation into cross-linked polymers synthe-
sized by TFRP conducted for many years did not betoken such a “burst” of interest.
Judging by the trends in publications on this issue, this new subfield has devel-
oped extremely fast: before 1997, only a few publications appeared per year, during
1997–1998 the number of publications increased to 100, and during 2000–2005
more than 250 articles and patents per year have appeared.
The first part of this book deals with TFRP with formation of cross-linked poly-
mers. It is based mainly on the results of systematic research of the authors and their
colleagues.
This part (Chapters 1 through 6) includes all available data (plus analysis of
these data) indicating the microheterogeneous character of TFRP. The microhetero-
geneous mechanism of TFRP includes both polymerization specifics at the ini-
tial, intermediate, and final stages (namely, initial formation, growth, and merger
of polymer grains performing the function of autonomous micro-reactors) and
structural and physical transformations in the course of TFRP (micro-syneresis,
microredistribution, and local glass transition).
The interpretation of the main kinetic regularities of polyunsaturated oligomer
polymerization in blocks and solutions and kinetic specifics of inhibited TFRP is
given taking into account the microheterogeneous mechanism of TFRP. The main
regularities of the polymerization of polyunsaturated compounds of vinyl and al-
lyl types in a film under the conditions of oxygen diffusion were explained in the
context of the proposed layer-by-layer TFRP model. A model of regular kinetically
active associates intended for interpreting kinetic abnormalities of oligo(acrylates)
and alkyl methacrylates polymerization is proposed: this model is substantiated
both kinetically and via computer simulation. Basic kinetic features of the three-
dimensional copolymerization of polyunsaturated (cross-linked) oligomers and mo-
nounsaturated (non-cross-linked) vinyl monomers were identified.
The main issues of the new branch in free-radical polymerization—namely,
“living” chain three-dimensional free-radical polymerization—are analyzed. Also,
exhaustive description is given for all studies on TFRP in the “living” chain mode
and the role of this mode for the macromolecular design of cross-linked polymers.
The new theory of gelation in the TFRP process, which was developed by
V. I. Irzhak and G.V. Korolev in 2000–2003, is described in depth. This theory is
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