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Book Review Carbocationic Polymerization. By J. P. Kennedy and E. Marchal

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non-chemists. The reviewer believes this statement to be
overoptimistic. Even chemists, who are not themselves experienced in nucleotide chemistry, will not directly be able
to synthesize, purify, analyze and enzymically ligate defined, oligonucleotide chains solely by having this excellent collection of experimental data at hand. However,
anyone who wishes to initiate work on the synthesis of
DNA is recommended to study this book.
Hubert Koster [NB 588 IE]
Carbocationic Polymerization. By J. P. Kennedy and E.
Marechal. John Wiley and Sons, Chichester 1982. xx,
510 pp., bound, L 55.50.
On the one hand, the technical preparation of polymers
by cationic polymerization is limited to a few monomers
e . g . isobutylene, vinyl ether and trioxane. On the other
hand, about 5-7% of all scientific publications on polymers are concerned with the mechanism, kinetics or thermodynamics of cationic homo- and copolymerization, with
monomer or oligomer synthesis.
It is, therefore, to be welcomed, that two competent authors, with many years of experience in the field, have now
produced a broad-based review of this constantly developing area.
The two introductory chapters pay special attention to
the individualities of cationic polymerization, as well as
explaining some general concepts and the nomenclature.
Compounds are defined as “cationic monomers” that are
“cationizable” and able to cationize other molecules of the
same compound, independent of whether a high molecular
weight polymer is formed thereby. About 200 compounds
(with few exceptions, unsaturated hydrocarbons), which
conform to this definition, are assembled in a table. Most
of them, however, only form oligomers. Unfortunately, literature references are not included in the table; the reader
is referred to an earlier book by J . P. Kennedy (Cationic
Polymerization of Olefins: A Critical Inventory; Wiley,
Chichester 1975). Further tables list commonly used initiators, of the Brmstedt acid, carbocation salt and FriedelCraft compound types. The chemistry of carbocationic polymerization is dealt with very thoroughly in Chapter 4.
For the most thoroughly investigated monomers such as
styrene, isobutylene, vinyl ether and some of the longer
chain a-olefins, the initiation reactions (including photoand electroinitiation), the propagation, termination and
transfer reactions and the “inifer method” developed by
Kennedy are described. The emphasis in all this is on the
chemical aspects. A relatively short chapter on kinetics follows.
Chapters 6 and 8 on the formation of copolymers are
worth particular mention. After a critical discussion of the
methods of parameter determination follows a table encompassing 643 polymerization systems (oxacycles are excluded) with r , and r2 values taken from the literature and
after recalculation according to the Kelen-Tiidos method.
Then follows a discussion of theoretical considerations for
the calculation of the reactivity together with the effect of
experimental conditions as well as of steric and electronic
factors. The chapter o n block and graft copolymers prepared by carbocationic reactions is very stimulating. The
chapter on “macromolecular engineering” conveys the impression that this field is in a state of flux and that all the
possibilities have not yet been exploited. The last chapter
gives a short outline of the industrial application and tech-
nical aspects with emphasis on polyisobutylene and polyvinyl ether. A short section by R . W. Lenz and J. E.
Chandler describes step-growth polymerizations proceeding via a Friedel-Craft alkylation mechanism, by reference
to a few examples.
Each chapter is accompanied by a comprehensive list of
references, arranged according to the authors (numbered
references would have been much more appropriate here).
The subject index is adequately comprehensive and very
helpful. The printing and formulae are good and free from
all but minor errors. The formulae on page 437 do not correspond to the text; isobutylene and PiB have to be substituted for styrene and PSt. The discussion of vinylamine on
page 33 is superfluous, since this monomer does not exist.
This book can be heartily recommended to all who are
active in polymer chemistry or who would like to achieve a
quick, comprehensive survey. It is to be desired that advanced students have access to it in their departmental libraries and are, thus, stimulated to study it.
Rolf C. Schulz [NB 590 IE]
Topics in Current Chemistry 103: Preparative Organic
Photochemistry. By P. Murgaretha. Springer Verlag, Berlin 1982. x, 89 pp., bound, DM 48.00.
The lively development of organic photochemistry and
its successful application in the synthesis of natural products makes a topical review of synthetically attractive phototransformations desirable. Margaretha attempts to supplement the book of the same title by A . Schonberg published in 1968. However, as the author states in the introduction, it would be a difficult task to present the current
state of organic photochemistry, which has, in the meantime, acquired an interdisciplinary character, according to
this example. A subjective selection has been made of the
plethora of examples of application and an attempt has
been made to fill in gaps in the literature. This has been
partially successful. This little book commands the attention of the practising chemist with a sceptical attitude to
photochemistry and, furthermore, it offers the beginner an
easy entry to the field.
After a general introduction to photochemistry follow
chapters on cleavage, addition and substitution reactions.
Next the multitude of rearrangements are treated as are
reactions with singlet oxygen. The book terminates with
references to experimental technique. The shortest possible, theoretical treatment of photochemistry in the introduction conveys some of the fascination of the mechanistic
aspects. The subjective choice of the examples has led to
some of the chapters being too short, so there are limits to
their representative nature. For example the subsection on
nitrogen extrusion, alongside the transformations treated
there are also important applications in the field of natural
product synthesis. It is also noticeable that the work of important groups, such as that of G . Berson, is not represented. A final criticism is concerned with the guidelines
contained in the addendum which summarize the experimental techniques. Because of their brevity they do not
contain very much information and do not refer to indispensable reference works like that of Culuert and Pitts.
In spite of the faults mentioned the book fulfils the desired aim. Its strength lies in the clear presentation which
quickly brings the reader into contact with the important
Angew. Chem. Int. Ed. Engl. 22 (1983) No. 6
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kennedy, carbocations, book, marchal, review, polymerization
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