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Book Review Houben-Weyl. Methoden der Organischen Chemie. Band E20 Teil 1Ц3 Makromolekulare Stoffe. Edited by H. Barte and J

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The value of having an index is not confined to textbooks;
its presence would also be appreciated in this conference
report. The price of the book is scarcely affordable for the
private purchaser, and the same remains true for our libraries with their meagre budgets.
Werner Guns [NB 948 IE]
Institut fur Physikalische Chemie
der Freien Universitiit Berlin
Houben-Weyl. Methoden der Organischen Chemie. Band
E 20, Teil 1-3: Makromolekulare Stoffe. Edited by
H.Bark and J. Falbe. Thieme, Stuttgart 1987. Part 1 :
lxxviii, pp. 1-688, bound, ISBN 3-13-219004-7; Part 2:
xxx, pp. 689-1794, bound, ISBN 3-13-219004-7; Part 3:
xxi, pp. 1795-2958, bound, ISBN 3-1 3-219004-7; price
for Parts 1-3: D M 3400.00 (subscription and pre-ordered
price: DM 3060.00).
There can hardly be a single chemistry library in the German-speaking world where “Houben-Weyl” is not to be
found. It is a standard work of reference with which one is
already familiar as a student, and which one reaches for
whenever it becomes necessary to master a new topic.
It is certainly remarkable that a quarter of a century ago,
under the series title “Methods of Organic Chemistry”, the
topic of “Macromolecular Substances” was already also included, in two volumes. The last twenty years have brought
far-reaching changes in the polymer field, creating a pressing
need for a revised version of this standard work. The breadth
of the areas to be covered makes it impossible for the revision
to be undertaken by only a small team of authors, let alone
by one. There is n o doubt that the editors have succeeded in
engaging the services of many eminent experts to rewrite the
different sections. There is a high degree of consistency in the
style of treatment, and in view of the number of authors (86!)
one may conclude from this that there has been a considerable amount of editing. Rules of nomenclature have been
followed to a sensible extent, which contributes a good deal
to easy readability.
The Part 1 volume is devoted entirely to preparative methods. A general introduction provides an easy entry into the
field for the chemist who is less familiar with polymers.
About 140 pages deal with the various methods for initiating
the polymerization of monomers with multiple C C bonds.
There is still much activity in this area, as shown by the fact
that in some articles over 50% of the citations refer to work
in the last ten years. Throughout the work as a whole the
high proportion of recent citations provides a good overview
of the main features of current research.
The largest amount of space is given to the description of
free radical initiation. In describing the initiation of polymerization by C C cleavage, by azo initiators, peroxides, diacylperoxides and percarbonates, new results are included,
and particular attention is given to systems with technological relevance. In addition to the conventional initiators, others such as the metal (0)compound/alkyl halide systems and
electrochemical initiation are described. The term “living
polymerization”, which is wrongly applied in the literature
to certain free radical polymerizations, I S here rejected as
being inaccurate, but to be consistent the section entitled
“Living free radicals” should have been called “Long-lived
free radicals”. Polymerization initiation using energetic and
high-intensity radiations is nowadays especiaIly important in
the manufacture of semiconductor chips and printed circuit
boards, and it is pleasing to find that this “laser polymer
chemistry” is described in detail.
firlugsgesellschufc mhH. 0-6940 Weinhrim, 1989
Cationic polymerization and living polymerization have
long seemed to be contradictory. This has changed. In the
account of the current position in anionic polymerization,
the main emphasis is on new results concerning ways of
influencing the microstructure of polydienes, functionalization, and influencing copolymerization parameters. In the
discussion of initiators for Ziegler-Natta coordination polymerization the current state of knowledge is summarized,
with particular attention to the technologically important
supported catalysts, to “linear low density” polyethylene,
and to influences on the microstructure of polydienes.
Group transfer polymerization is now just five years old, and
the progress made on this topic is shown by a wealth of new
The theory of copolymerization is discussed from the
standpoint of its practical applicability by the preparative
Over 200 pages are devoted to polymerization methods;
particular emphasis is laid on technical polymerization procedures, as in bulk polymerization, and in solution, emulsion, suspension, precipitation and gas phase polymerization
methods. Emulsion polymerization (approx. 100 pp.) is
treated theoretically, and the colloidal properties of the
products, such as the stability of the emulsions, coagulation
and film formation, are reviewed. In the section on suspension polymerization the technologically important Pickering
dispersing agents are discussed, as is also the synthesis of
macroporous supports. Fluid bed processes for the polymerization of formaldehyde or ethylene are found under the
heading “Gas phase polymerization”. The equipment required for plasma polymerization and the capabilities of the
method are also described. Solid phase polymerization and
polymerization in thin films allow ordered systems to be
produced. In addition to the classical case of diacetylene
polymerization, polymerization in perovskites, inclusion
compounds and ultrathin films are described.
The synthesis of carbon-heteroatom polymers is treated in
the chapters that deal with the polymerization of monomers
with CO o r C N multiple bonds and with ring-opening polymerizations. The number of heterocyclic compounds that
have been used in ring-opening polymerizations has grown
enormously in the last 25 years; a short section is devoted to
the free radical polymerization of heterocycles, but the main
emphasis in this chapter is on the cationic and anionic ringopening polymerization of heterocycles. The mechanistic aspects of the polymerization of oxacycles and lactones are
clearly set out. Access to the literature on the copolymerization behavior of cyclic ethers is facilitated by the inclusion of
more than 50 references.
In the chapter on “Polyadditions” the main emphasis is on
polyurethane chemistry. The problems of synthesizing
oligourethanes of uniform molecular structure are discussed
in detail. The notion which Otto Buyer introduced of tailored
synthesis in polyurethane chemistry is discussed, taking as an
example the synthesis of segmented polyurethane elastomers. Other topics treated are the silane/olefin addition
and the applications of the Diels-Alder reaction. Notwithstanding the enormous importance of the diisocyanate/diol
reaction, the potential underlying the principle of polyaddition is still far from being exhausted.
The chapter on “Polycondensations” begins with a very
comprehensive survey of the known structure-building reactions, but unfortunately no critical evaluation of yields and
side-reactions is included. The prepolymer technique, which
is especially suitable for synthesizing crosslinked polymers, is
described in detail in accordance with its practical importance. Considerable space is also given to the description of
Angew. Chem. Inf. Ed. Engl. 2X [ 19891 No. 5
ordered structures in polycondensates in the form of segmented or block copolymers. The section on structure-property relationships is especially valuable for the preparative
chemist. However, the generalizations that are made, e.g.
concerning T, and Tm,should only be regarded as approximate rules with many exceptions. The problems and the advantages and disadvantages of polycondensation in melts, in
solutions and on surfaces are thoroughly discussed.
In considering reactions on macromolecules as a method
of synthesis, the importance of the effects of neighboring
groups on the structure of the polymer thus formed is usually
underestimated. This chapter provides a good overview of
this topic. Graft polymerization reactions offer a wide range
of possibilities for modifying polymers, and are used in many
different forms in industrial processes. In this article the
choice of a suitable initiator for a given graft polymerization
system is clearly explained.
The final chapter of the Part 1 volume describes modifications obtained by combining polymers. As well as interpenetrating networks, polymer blends offer ways of combining
properties to achieve a desired result. The principles of producing modified polymers with high impact strength and
thermoplastic elastomers are described.
In the Part 2 and Part 3 volumes the emphasis is on the
different chemical classes of macromolecular substances.
Over 100 pages are devoted to the polymerization of olefins,
and the various methods are critically evaluated. Many laboratory recipes for both homo- and copolymerization are
given. The densely packed information ranges from phase
diagrams to safety aspects. Questions such as which
comonomers should be used to stabilize an emulsion or to
improve the adhesion strength of a film are answered, as well
as those relating to ways of obtaining higher stereospecificity
in the polymerization of propene. Under diene polymerization (over 100 pp.) the main emphasis is on microstructure,
but in addition reaction regulators, and modifications
through copolymerization and incorporating stabilizers are
discussed. Metathesis reactions can nowadays be carried out
as a form of living polymerization. However, many questions concerning the stereochemistry still remain unanswered. Here the current state of knowledge in this area is
carefully set out. The section on “Styrene polymerization”
concentrates on modifications, e.g. by copolymerization,
grafting or ionic block copolymerization. It is remarkable
that over 90% of the citations refer to the period since the
publication of the previous edition. In addition fluoroolefins, chloroolefins, vinyl ethers, vinyl esters, unsaturated
aldehydes and acrylic compounds as monomers are carefully
and expertly discussed. Polymerization reactions of
acetylenic monomers are not confined to acetylene itselfdetails of the polymerization of more than 40 acetylene
derivatives are included. Diines too undergo polyaddition
reactions to give many different polymers. Aliphatic and
aromatic polyethers and aliphatic polyacetals are polymers
that exhibit a very wide range of properties profiles. For
these the importance of including alongside the polymerization processes the properties of the resulting polymers has
been recognized, and representative data on technical products are also listed.
Polyesters in all their many variants are described in
50 pages. In addition to the familiar aryl-aliphatic polyesters
there are detailed descriptions of unsaturated polyester
resins, alkyd resins and polycarbonates. Sulfur-containing
aliphatic and aromatic polymers are treated in the following
chapter. These too include products of basically different
types: on the one hand alternating copolymers of olefins and
sulfur dioxide formed by free radical polymerization, which
Angew. C ‘ h m i .
Inr. Ed. Engl. 28 (1989) No. S
degrade easily as indicated by their low ceiling temperatures,
and on the other hand high performance materials such as
polyphenylenesulfide and polyphenylenesulfone.
In the area of polymers with main-chain nitrogen atoms
the longest chapters are those on polyamides, polyurethanes
and polyureas. The chapter on “Polyamides” deals with various polyheterocycles including polyimides, polyamidimides
and polyether-imides, some of which also appear in Part 3
under the heading “Special polymers”. Considerable advances have been made in the last 25 years in the field of
ionomeric polyurethanes, and accordingly the preparative
aspects of introducing ionic groups are discussed. In these
150 pages on polyurethanes an impressive account is given of
the many possible variations of the molecular architecture.
Other chapters in this volume are devoted to polymers with
P, B, Si and metals as heteroatoms.
In the Part 3 volume phenolic and amino resins are described. In order to tailor the properties profile of formaldehyde resins to suit the many different applications a detailed
knowledge of the basic reaction steps is essential. The short
synopsis of areas of application given here is very useful. Epoxide resins are now more than 40 years old. In addition to their best known area of application in high performance composites, the wide range of variations that are
possible in the underlying chemistry of starting materials
and curing agents, as described here, opens up many different areas of use, e.g. in paints and other surface treatments.
The long third chapter of Part 3 (200 pp.) recognizes the
enormous practical importance of the production of chemically modified polymers. The treatment is divided into synthetic polymers and polysaccharides. Under synthetic polymers a number of reactions have had to be omitted because
of the need to be selective; those sacrificed include hydrolysis
of esters and amides, imidization reactions and cyclization
reactions in general. However, this still leaves a very wide
range of topics. The conversion of polysaccharides is one of
the oldest processes of polymer chemistry. Under the heading “Renewable raw materials” this has again become an
important topic today. After a general discussion of structure-property relationships as influenced by the complex
pattern of substitution, individual groups of cellulose ethers
and cellulose esters are discussed. Special sections are devoted to starch and guarane derivatives.
In the next chapter we return to polymers produced by
synthetic reactions. This chapter, on “Special polymers”, is
very varied in content. The topics covered are polymers
formed by condensed heterocyclic rings, products from polymerization of ketene, polymers from carbon dioxide, liquid
crystal polymers, chirdl polymers and inorganic polymer
chains. The section on “Condensed heterocyclic rings” is a
good survey of the high temperature polymers known at
present. That on “Liquid crystal polymers” suffers a little
from the fact that aromatic polyesters and amides are treated
elsewhere. The section on “Chiral polymers” consists of only
one table. Under the heading “Inorganic polymers”,
polyphosphazenes, polyorganosilanes, silicones and polymers synthesized from metal phthalocyanines are described.
A considerable amount of space is given to characterization methods. Although the determination of chemical constitution by decomposition has nowadays become less important compared with spectroscopic methods, the analysis
of end groups remains a problem, and this chapter offers
some help in that respect. In the section on “Physical methods of polymer characterization”, difficulties that may be
encountered are briefly summarized and references are given
for more detailed reading.
$3 VCH Vcrlags~esellschaltmbH, 0-6940 Weinhelm, 1989
The final chapter of the work is concerned with toxicology
and with environmental aspects of polymers. This is followed by a bibliography (approx. 100 pp.) listing further
literature, mainly reviews, under the individual chapter
headings. It is doubtful whether a reader who only makes
occasional use of the work will find this additional material;
perhaps it should have been put after the introduction or at
the ends of the chapters.
As so often happens, there are problems with the subject
index. One is used to looking for polystyrene (Polystyrol)
under “Poly . . _ ”After
realizing that one must look under
“Styrol”, further difficulties arise with “Polyethersulfon”. as
here one has to search under “Sulfon”: however, “Polyetherketon” does not appear under either “Etherketon” o r
The work contains hardly any printing errors, and the
typography and presentation are attractive. There are a few
errors which are likely to cause a smile: “Schmutzkolloide”
on p. 188; in the contents list and in the index the SmithEbert theory appears instead of the emulsion theory, and on
p. LIV under “General articles on large molecules” the
“Encyclopedia of Polymer Science and Technology” is also
The few shortcomings are small when weighed against the
scientific value of the work. As an up-to-date work of reference for all scientists involved in polymer chemistry it is
indispensable, and it will soon find its place in the libraries of
polymer science departments and institutes. However, for
those universities where macromolecular chemistry is not
strongly represented the price may prove to be a serious
Walter Heitz [NB 945 IE]
Fachbereich Physikalische Chemie
der Universitat Marburg (FRG)
One Pioneer or Several Pioneers? The Discovery of
Noble-Gas Compounds
P. Laszlo and G. J. Schrobilgen have submitted the following
Addendum to their article on noble-gas compounds (Angew.
Chem. 100 (1988)495; Angew. Chem. Int. Ed. Engl. 27(1988)
A letter from Henry Selig of August 29, 1988,[*]differs in
the sequence of events, in respect to a key finding, from John
Malm’s recollections, which we had no reason to doubt and
have followed in our account. In Dr. Selig’s words: “. . . most
members of the Argonne fluorine research group had gone to
the Estes Park, Colorado, fluorine symposium leaving
Claassen, Maim and myself behind. The actual experiment
was planned by the three of us and carried out during that
week. On the day of the very first experiment, Friday, Au-
To Prof. Lusrlo (note added by the editorial staff).
gust 2, 1962 John Malm was at home ill and Claassen and I
conducted the experiment by heating Xe F,in a nickel can
at 400 “C. After pumping off the volatile materials and not
finding any xenon we were still sceptical. We phoned Malm
at home to apprise him of the results. The following week we
identified the material in the weighing can as XeF,, presenting our colleagues returning from Estes Park with a fait
We gratefully acknowledge Dr. Selig’s version of the first
synthesis of XeF, at Argonne, an interesting variant with
respect to the story we had reported. Our account, let us
remind the readers, has as its main focus the prehistory of the
discovery of noble-gas compounds.
Prof. P. Laszlo
Laboratoire de Chimie, Ecole Polytechnique
F-92 128 Palaiseau Cedex (France)
Prof. G. J. Schrobilgen
Department of Chemistry, McMaster University
Hamilton, Ontario L8S 4M1 (Canada)
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Angen. Chem. lnt. Ed. Engl. 28 (1989) No. 5
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