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This review is focused on controlled/living radical polymerization methods for the preparation of various copolymers. A brief introduction to the subject of radical polymerization, and early attempts to control it, is followed by a detailed examination of the literautre on controlled/living radical copolymerizations from the mid-90's until 2001. The topics covered include statistical/gradient, block, graft, and star copolymers and the polymerization methods used to produce them. These copolymers were prepared using three major controlled radical methods (either nitroxide mediated polymerization, atom transfer radical polymerization or degenerative transfer) and a combination of polymerization techniques, including transformation chemistry or the simultaneous/dual living polymerizations, to achieve the desired chain architecture or topology. An evaluation of the current state of the field is also presented.
The progress in polymer science is revealed in the chapters of
"Polymer Science: A Comprehensive Reference." In Volume 1, this is
reflected in the improved understanding of the properties of
polymers in solution, in bulk and in confined situations such as in
thin films. Volume 2 addresses new characterization techniques,
such as high resolution optical microscopy, scanning probe
microscopy and other procedures for surface and interface
characterization. Volume 3 presents the great progress achieved in
precise synthetic polymerization techniques for vinyl monomers to
control macromolecular architecture: the development of metallocene
and post-metallocene catalysis for olefin polymerization, new ionic
polymerization procedures, and atom transfer radical
polymerization, nitroxide mediated polymerization, and reversible
addition-fragmentation chain transfer systems as the most often
used controlled/living radical polymerization methods. Volume 4 is
devoted to kinetics, mechanisms and applications of ring opening
polymerization of heterocyclic monomers and cycloolefins (ROMP), as
well as to various less common polymerization techniques.
Polycondensation and non-chain polymerizations, including dendrimer
synthesis and various "click" procedures, are covered in Volume 5.
Volume 6 focuses on several aspects of controlled macromolecular
architectures and soft nano-objects including hybrids and
bioconjugates. Many of the achievements would have not been
possible without new characterization techniques like AFM that
allowed direct imaging of single molecules and nano-objects with a
precision available only recently. An entirely new aspect in
polymer science is based on the combination of bottom-up methods
such as polymer synthesis and molecularly programmed self-assembly
with top-down structuring such as lithography and surface
templating, as presented in Volume 7. It encompasses polymer and
nanoparticle assembly in bulk and under confined conditions or
influenced by an external field, including thin films,
inorganic-organic hybrids, or nanofibers. Volume 8 expands these
concepts focusing on applications in advanced technologies, e.g. in
electronic industry and centers on combination with top down
approach and functional properties like conductivity. Another type
of functionality that is of rapidly increasing importance in
polymer science is introduced in volume 9. It deals with various
aspects of polymers in biology and medicine, including the response
of living cells and tissue to the contact with biofunctional
particles and surfaces. The last volume is devoted to the scope and
potential provided by environmentally benign and green polymers, as
well as energy-related polymers. They discuss new technologies
needed for a sustainable economy in our world of limited resources.
Provides broad and in-depth coverage of all aspects of polymer
science from synthesis/polymerization, properties, and
characterization methods and techniques to nanostructures,
sustainability and energy, and biomedical uses of polymersProvides
a definitive source for those entering or researching in this area
by integrating the multidisciplinary aspects of the science into
one unique, up-to-date reference workElectronic version has
complete cross-referencing and multi-media componentsVolume editors
are world experts in their field (including a Nobel Prize winner)
This unified presentation of cationic polymerization discusses
initiation, propagation, transfer, and termination in cationic
polymerizations of alkenes and heterocycles. It also elucidates the
mechanisms of the reactions involved in all carbocationic and
ring-opening polymerizations. It is written by internationally
acclaimed experts in their respective fields.
The design and the realisation of well defined polymer
architectures has become an important goal in macromolecular
science. The prerequisite for achieving this goal is the
availability of controlled polymerisation reactions. Living anionic
polymerisation was the first reaction fulfilling these
requirements. Cationic polymerisation only came into play when it
was realised that it was possible to create an equilibrium between
active and dormant species with the fraction of the dormant species
being far superior to that of active ones. A corresponding
principle applies to controlled radical polymerisation per formed
in quite a number of modes such as nitroxide mediated
polymerisation (NMP), atom transfer radical polymerisation (ATRP),
reversible addition frag mentation chain transfer (RAFT) or
catalytic chain transfer (CCT) reactions. All of these variants of
controlled radical polymerisation lead to well defined archi
tectures with the particular advantage that a much larger number of
monomers are suitable and the reaction conditions are much less
demanding than those of living ionic polymerisation reactions.
Although in controlled radical polymerisation, termination
reactions cannot be excluded completely, they are limited in their
extent and consequently the mol ecular weight is controlled, the
polydispersity index is small and functionalities can be attached
to the macromolecules. These features are indicative of the real
isation of well defined polymer architectures such as block
copolymers, star shaped and comb shaped copolymers.
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