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Book Review Encyclopedia of Polymer Science and Technology. Plastics Resins Rubbers Fibers. Edited by H. F. Mark N. G. Gaylord and N. M

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chemistry became the basis of soaring chemical research,
emphasized by the founding of the first dyestuff factory.
Only a few reflections are devoted to the subsequent stormy
and restless era. How many surprises does the future hold perhaps the creation of psychological chemistry enabling
man to act on his psyche?
The author has had a difficult task in condensing the historical development into so little space and yet giving the
most important events their due attention. Critical selection
became essential, and the author has succeeded by interposing anecdotes and by the use of a flowing style to make
the actors of the exciting drama appear before our eyes in
the atmosphere of their own age.
This small volume will instruct the layman in a friendly
manner and will relate many new things or put old ones in
perspective to the initiated. Once begun, the book will not
be put down before the last page is read.
J . Rigaudy
[NB 655 IE]
Solvent Effects on Reaction Rates and Mechanisms. By E. S.
Amis. Academic Press, New York/London 1966. 1st Edit.,
xi, 326 pp., numerous figures a n d - t a e s T l 0 . 5 0 .
Although M . Rerthelo! and L. de St. Gilles observed and
studied the effect of solvents on the rate of chemical reactions
as long ago as 1862, and N . Menshutkin stated in a fundamental work published in 1887 that “a reaction is inseparable from
the medium in which i t takes place”, no critical compilation
of the extensive experimental and theoretical work o n the
effects of solvents on reaction rates and mechanisms has
appeared until the present monograph by E. S. Amis.
The first four chapters form theoretical attempts to interpret
the effect of solvents on reactions involving different electric
charges (reactions between ions, dipolar molecules, dipolar
molecules and ions, and also electron exchange reactions between ions). Chapter V is devoted to the effect of external and
internal pressure (cohesion) in addition to the comparison
between gas-phase and solution reactions, and also the
effect of solvent viscosity on the above types of reactions.
Insofar as they describe the effect of the solvent on the
reaction rate empirically, linear free energy relationships
are listed in the following chapter.
The last two chapters deal with the qualitative solvation
model proposed by E. D . Hughes and C. K. Ingold and also
with further special solvent effects such as selective solvation,
cage effects, primary and secondary salt effects, and hydrogen
bonding.
The presentation of the often complex material is interspersed
with numerous examples, 26 illustrations, and 30 tables.
Theoretical physical aspects are emphasized rather than
chemical ones. Considering the scope of the subject, it is
perhaps inevitable that some aspects of particular importance
to the organic chemist have been left out. No indications are
given of the great importance which the dipolar, aprotic
solvents have achieved in nucleophilic and electrophilic
substitution reactions (A. J. Parker), or of the control of the
reactivity of ambident anions and cations by the solvent
( N . Kornblum). The value of the detailed bibliography (about
500 references, in part complete to 1965) is unfortunately
marred by numerous misprints (e.g. references 16, 18 (p. 29);
33 (p. 57); 48, 56, 59, 65, 74 (pp. 119-120); 4, 6, 11, 15, 36,
41 (pp. 145-146); 8, 43 (pp. 181-182); 24, 25, 80, 108, 110,
113, 135, 136, 153, 157, 166 (pp. 251-255)). Some equations
are badly set out typographically or actually wrong (e.g. eqs.
2.67; 5.16; 7.16; 7.17; 7.18; 7.124; 7.132; 7.143 and 7.144).
No strict differentiation is made between mesomerism and
equilibrium arrows.
In all, the book is suitable both as an introduction and for
further study by inorganic and organic chemists. Its use is
facilitated by good author and subject indexes, and it can
serve as a valuable aid”to discussing the rates and the mechanisms of chemical reactions in solution.
C. Reichardt
m B 647 IE]
158
Oxidation in Organic Chemistry. Edited by K . R. CViberp.
From the series of monographs “Organic Chemistry”, Vol.
5. Part A. Academic Press, New York-London 1966. 1st
Edit., xi, 443 pages, $ 14.00.
Those who are familiar with the excellent reviews in “Neuere
Methoden der praparativen organischen Chemie” will welcome this English-language collection of critical reviews of
the literature on selective methods. Oxidizing agents are still
among the most important reagents of organic chemistry,
and a general need will be filled by the two volumes (the
second is in preparation) devoted to this field by the publishers of “Organic Chemistry”, a collection of monographs
published since 1964.
The first part of this book includes oxidation with permanganate ( R . Stewart), with chromic acid and chromyl compounds
( K . B. Wiberg), with vanadium(v), cobalt(Irr), and manganese(m) (W. A . Waters and J . S. Littler), with cerium ions
(W. H . Richardson), and with lead tetraacetate ( R . Criegee),
as well as the cleavage of glycols (C. A . Bunton). All the
known experimental results are included, as well as the theoretical principles, the solvents and reaction conditions used,
and the inorganic and particularly the organic substrates t o
be oxidized. In some cases extensive tables of kinetic data,
and occasionally even laboratory procedures, are given. The
largest sections are naturally those dealing with topics of
interest to the preparative organic chemist. The present
volume may therefore be described as the most up-to-date
and comprehensive work of its kind, and will prove a valuable
aid to any chemist. The uniform layout of the six chapters
and the detailed subject and author index are excellent.
G. Anner
[NB 616 IE]
Encyclopedia of Polymer Science and Technology. Plastics,
Resins, Rubbers, Fibers. Edited by H. F. Mark, N . G .
Gaylord, and N . M. Bikales. Vo!. 2: Amino Resins to
Casein. Interscience Publishers, a Division of John z i l e y &
1965. 1st Edit., xiii, 871
---Sons, New York-London-Sydney,
- ..........
pp., many illustrations and tables, single copies 375 s;
subscription price 300s.
The second volume of this handbook [*I contains 41 contributions; most of the authors are active in industry in the
United States. The diversity of the subject matter is demonstrated by the following details.
“Amino Resins” is the heading of a n admirably illustrated
article (94 pp., 101 references), which deals not only with the
basic reactions of this class of compounds, but also delves
deeply into the technical side of the subject. The production
of polymers is treated in the sections entitled “Anionic Polymerization” (143 references; important advances made in
1963 and 1964 are unfortunately omitted), “Block and Graft
Copolymers” (44 pp., 254 references, preparation, properties,
and uses of these copolymers), “Cage Effect” (6 pp. paying
special attention to phenomena which appear during polymerization), and “Bulk Polymerization” (24 p ~ . ,82 references). In the last named article the heat of polymerization of
vinyl chloride is given as 14.4-16.7 kcal mole-’ without any
comment of the sort that one would expect to accompany
such a wide range of values; furthermore, the table of densities of monomers leaves much to be desired.
The contribution headed “Antibodies and Antigens” is
rather brief (only 12 pages) in view of the general importance
of this field of study. On the other hand, the wealth of wellarranged material in “Biocides” make this contribution
really exemplary. The copious list of commercially available
stabiIizers in the article “Antioxidants“ is also very welcome;
a similar list is missed in “Antistatic Agents” (25 pp.). Although “Aqueous Polymerization” (144 references, 37 pp.)
gives a good summary of the widely varying types of initiators, information concerning the water solubility of the monomers at various temperatures is rather sparse.
[*I Cf. Angew. Chem. 78, 156 (1966); Angew. Chem. internat.
Edit. 5 , 148 (1966).
Angew. Chem. internat. Edit. 1 Yol. 7 (1968) No. 2
,,
Problems of a more technical nature are covered in the sections headed “Annealing” (rather brief, having only 13 pages),
“Automotive Applications” (12 pp.), “Bag Molding” (17pp.),
“Belting” (12 pp.), “Biaxial Orientation” (34 pp., several
illustrations), “Bituminous Materials” (36 pp., 18 tables),
“Bleaching” (46 pp., much information concerning apparatus), “Blowing Agents” (detailed information concerning the
applicability of various classes of compound as foaming
agents), “Building and Construction Applications” (with
several illustrations taken from practice), “Calendering”
(19 pp.), and “Casein” (1 3 pp.).
Special polymers are dealt with in the contributions headed
“Bicycloheptene and -heptadiene Polymers” (the tabular
summaries are worthy of praise; the literature is covered up
to the end of 1964), “Butadiene Derivatives, Polymeric”
(12 pp., 87 references), “Butadiene Poiymers” (76 pp., 262
references), “Butylene Polymers” (40 pp., 79 references), and
“N-Carboxyanhydrides”. Strangely, the copolymers are not
mentioned at all in the section o n butadiene derivatives and
onIy very briefly in that o n butyfene polymers; the table of
r-values of the copolymerization of butadiene could well be
more complete. In the articles concerned with individual
polymers the reviewer missed lists of trade names and would
therefore venture to suggest that the following editions
should include tables in which the various polymers are
listed alphabetically, both under their commercial designations and their systematic names.
Information about auxiliary agents for polymerization and
for the polymerizate is given under the headings “Antiozonants” (8 pp.), “Azo Catalysts” (very detailed tables listing
characteristic properties of 71 azo compounds), “Antifoaming Agents” (8 pp.), and “Brighteners, Optical” (9 pp.). The
definitions of terms such as “A-Stage’’ and “B-Stage”, which
refer to the production of thermosetting resins, are given in
merely 2 and 4 lines, respectively (without examples). The
diffusion of gases through polymer films is treated in “Barriers, Vapor” (13 pp.). Finally, mention should be made of
the chapters entitled “Boron Compounds” (16 pp., many
pieces of information about the compounds of boron),
“Bagasse” (5 pp.), and “Carbon” (18 pp. devoted to a discussion of the most important types of soot).
Apart from the main headings listed above there are of
course others; for example, in the present work alone, the
contribution “Biocides” is given under a further four headings. This kind of subdivision greatly facilitates use of the
book.
0 .Fuchs
[NB 623a I € ]
Encyclopedia of Polymer Science and Technology. Plastics,
Resins, Rubbers, Fibers. Edited by H . F. Mark, N. G . Gaylord, and N . M . Bikales. Volume 3: Casting to Cohesive
Energy. Interscience Publishers, a division of John Wiley &
Sons, New York-London-Sydney 1965. 1st Edit., xiii,
862 pp., numerous illustrations and tables. Single copies
375 s; subscription price 300 s.
More than half of the third volume (28 contributions from
48 authors) of this work is devoted to cellulose and its
derivatives. The treatment of cellulose itself covers 97 pages
and includes 436 references; the most important physical
and chemical properties are well presented in 56 figures and
18 tables. Some overlapping does, however, occur between
this article and those entitled “Cellulose, Biosynthesis”
(13 pages, 43 references), “Cellulose, Graft Copolymers”
(44 pages, 81 references, including impressive photomicrographs and author’s [Imrnergut]unpublished results), “Cellulose Derivatives” (17 pages, in which only the “non-classical”
cellulose derivatives such as deoxy-, aminodeoxy-, halogenodeoxy-cellulose, etc. and oxidized cellulose and derivatives
are treated), “Cellulose, Microcrystalline” (7 pages), and
“Cellulose, Analytical Methods” (too short with 5 pages).
If such repetition had been avoided, much more space could
have been devoted to other sections.
Angew. Chem. internat. Edit. 1 Val. 7 (1968) / No. 2
Cellulose foil is dealt with in the chapter entitled “Cellophane” (20 pages, 150 references, production, applications) ;
the firm [Krrlle] which owns the trade mark Cellophan, is not
mentioned although the names of three American manufacturers are given. Further subject headings are: “Cellulose
Esters, Inorganic” (18 pages on nitrates, half a page on other
esters; no table showing the dependence of solubility on the
degree of nitration is given). “Cellulose Esters, Organic”
subdivided into “Manupacture” (28 pages, 102 references,
good tabular summaries), “Plastics” (66 pages, 74 references;
although emphasis is placed o n technological aspects, properties are summarized in large tables), “Fibers” (56 pages
describing production and applications, 58 references; tables
extending over many pages give trade names - a feature
that is often neglected), and “Miscellaneous Cellulose
Esters” (4 pages). “Cellulose Ethers” (91 pages, 181 references) with the main divisions ethyl, methyl, hydroxyalkylmethyl, hydroxyethyl, sodium carboxymethyl, cyanomethyl,
and carbamoylethyl-cellulose, as well as other cellulose
ethers; most of these contributions d o not contain a clear
representation of the solubility and plasticizing properties
that are so important in practice.
Material concerning the manufacture of polymers and polymerization kinetics is provided in the sections “Cationic
Polymerization” (25 pages, 66 references; although the
mechanism is treated thoroughly only a selection of catalysts
is given), “Catalysis” (short description of methods for the
production of macromolecules, 9 pages), “Ceiling Temperature” (too short with one page, only four examples,
literature not covered beyond 1958), “Chain Reaction Polymerization” (26 pages, 112 references; in this section and in
the one entitled “Catalysis” Ziegler catalysts are treated
briefly but a full treatment will not appear until the last
volume), “Chain Transfer” (30 pages, 126 references; determination of transfer constants with results, special technical
applications), and “Chemically Resistant Polymers” (30
pages, 57 references including many from the years 1963 and
1964, particular attention being given to polymers suitable
for use in rocket technology).
Applications of a technical nature are dealt with in the
sections entitled Casting” (20 pages, contains superfluous
illustrations), “Coating Methods” (69 pages, comprehensive
descriptions of methods involved, 89 illustrations), and
“Cellular Materials” (51 pages, 152 references, processes,
statistical data, properties). The individual types of polychloroprenes are described in “2-Chlorobutadiene Polymers” (36 pages, 79 references, production, applications,
etc.).
Analytical methods are given in the following sections:
“Characterization of Polymers” (21 pages, 77 references,
some characteristic structural features such as branching,
sequence length distribution in block copolymers, problems
of determining chemical non-uniformity, head to head structures, foreign groups, and networks are merely touched
upon, if mentioned at all), “Chemical Analysis” (34 pages,
197 references, physical methods such as I R and N M R
speccometry and differential thermal analysis are given in
addition to chemical methods), and “Chromatography”
(32 pages, 76 references, methods, examples). “Castor Oil”
(6 pages) and “Chitin” (11 pages) are treated as individual
compounds. A section headed “Cohesive-Energy Density”
(30 pages, 75 references covering the literature up to 1964,
tables of solubility parameters for low and high molecularweight compounds, special cases of compounds containing
strongly polar groups) concludes the volume under review.
To summarize it may be said that this volume, like its
predecessors, contains a wealth of data from the field of
polymer science, which can otherwise be found only by
searching the specialized literature. In view of the rapid
development of the science and technology of macromolecular materials the encyclopedia represents a valuable source
of information for workers in this field.
0. Fuchs
[NB 623b IE]
159
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