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Chemistry and Applications of Polyphosphazenes. By Harry R. Allcock

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graphs in the area. Special attention is
given to recent developments within the
area of metal-catalyzed reactions.
In conclusion, this book provides an
excellent overview of synthetic applications of 1,3-dipolar cycloaddition reactions since 1984. Although some overlapping in the field of recent developments in metal-mediated cycloaddition
reactions is apparent, all the chapters of
the book are well written with few
typographical errors and extensive references. This volume is highly recommended for all scientific libraries, and as
a very useful desk reference for all those
concerned with 1,3-dipolar cycloaddition reactions, and for anyone wishing to
utilize these reactions for organic synthesis of heterocycles and natural products.
Hiroyuki Suga
Shinshu University
Wakasato, Nagano (Japan)
Chemistry and Applications of
By Harry R. Allcock.
New York 2003.
725 pp., hardcover
E 379.00.—ISBN
The polyphosphazenes are a unique
class of inorganic polymers that contain
alternating phosphorus and nitrogen
atoms in the main chain. The earliest
[NPCl2]n, dates back to the work of
Stokes late in the nineteenth century,
making it amongst the earliest synthetic
macromolecules. Today, research on
phosphazene-based materials continues
to thrive and expand, and it is now more
than 100 years since their first mention.
This book provides a comprehensive
overview of the state of the art in
research on these fascinating materials,
which rival silicones as one of the two
most important classes of inorganic
polymers. The author, Professor
Harry R. Allcock, is a world authority
on phosphazene chemistry and has been
a pioneer in the development and
growth of this field. The author points
out that “because of the enormous
breadth of the field, no single volume
can cover the entire subject in detail.”
Allcock has come very close to achieving that.
Chemistry and Applications of Polyphosphazenes will be a welcome addition to the bookshelves of researchers
interested in Main Group or polymer
chemistry, and is the first book dedicated solely to phosphazene high-molecular-weight polymers. It is logically
organized into three main sections,
each consisting of several chapters covering specific aspects of this chemistry.
Each chapter is thoroughly referenced
to the primary literature or patents, and
over 1000 citations are provided. An
excellent index and table of contents
allow the reader to quickly navigate the
various topics.
The introductory section provides
information on nomenclature and a
general overview of the synthetic
approaches to phosphazene high-molecular-weight polymers, and explains the
idea of using well-defined molecular
species as models for the high-molecular-weight polymers. The second major
component of the text deals with the
synthetic methodologies used to prepare
polyphosphazenes. Included here are
chapters outlining the synthesis of the
cyclic trimeric monomers (i.e., N3P3Cl6),
the use of thermal ring-opening polymerization methods, and the exciting
recent advances in condensation polymerizations. The macromolecular substitution approach, unique to polyphosphazenes, is treated in detail. In addition, efforts toward the preparation of
cyclophosphazene-containing polymers
and phosphazene-hybrid organic poly-
0 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
mers are described. The third and final
section of the book deals with the
remarkable and diverse properties of
phosphazene polymers. Potential applications are treated in the chapters on
biomaterials, membranes, solid polymer
electrolytes, optical polymers, and elastomers. Uses in products such as dental
liners, fuel lines, and flame retardant
fabrics illustrate the exciting prospects
for these materials. Throughout, Allcock emphasizes how the material properties can be tailored through sidegroup modification and cross-linking.
One aspect that could have received
more attention is the fascinating subject
of bonding in phosphazene molecules
and polymers. The role of d orbitals in
forming the skeletal PN backbone of
polyphosphazenes is still under debate.
Therefore, it is unfortunate that fewer
than ten pages, spread over two chapters, were devoted to this topic. Perhaps
a separate chapter treating bonding
theories would have been more appropriate.
The book contains numerous blackand-white photographs and excellent
illustrations. The selective use of color,
particularly in the applications section,
would have enhanced the visual quality
of the book. A very useful feature, from
a practical point of view, is the inclusion
of sections entitled “experimental considerations”. The detailed procedures
given and the photographs showing the
experimental setup are not only helpful
for the practicing researcher, but in
some cases are suitable for use as
undergraduate inorganic laboratory
Overall, this is an excellent and
much needed monograph on a fascinating subject that blends inorganic and
polymer chemistry. I recommend it
Derek P. Gates
Department of Chemistry
University of British Columbia
Vancouver (Canada)
DOI: 10.1002/anie.200385981
Angew. Chem. Int. Ed. 2003, 42, 4569 – 4570
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chemistry, application, allcock, polyphosphazenes, harry
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