An Introduction to the CHEMISTRY of the SILICONES By EUGENE G.
ROCHOW Research Laboratory, General Electric Company NEW YORK JOHN
WILEY SONS, INC. LONDON CHAPMAN HALL, LIMITED COPYRIGHT, 1946 BY
EUGENE G. ROCHOW AU Rights Reserved This book or any part thereof
must not be reproduced in any form without the written permission
of the publisher. SECOND PRINTING, MARCH, 1947 PRINTED IN THE
UNITED STATES OF AMERICA To P. G. F. PREFACE The organic compounds
of silicon, which have been the subject of many scholarly
researches during the past 80 years, at last show promise of
emerging from the laboratory and finding a place in industry. An
understanding of the behavior of organosilicon materials is
necessary to their intelligent use and, inasmuch as the chemistry
of these substances ordinarily is not treated in our textbooks, it
is possible that a compact yet comprehensive survey of our present
knowledge in this field would be of service to chemists, engineers,
and industrial designers. This volume has just such a purpose. The
first few chapters review the silanes and their derivatives in some
detail, in order to provide an understanding of the fundamental
chemistry of the nonsilicate com pounds of silicon. The later
chapters emphasize the silicone polymers which have achieved
commercial importance and deal with the methods for their
preparation, their chemical and physical properties, and their
possible usas. The processes available for large-scale production
are treated separately, and a review of methods of analysis is
included. In order not to burden the text with definitions and
explanations of nomenclature which might already be familiar to
some readers, an extensive glossary of terms isappended. An
exhaustive review of the literature on organic compounds of sili
con cannot very well be included in a volume intended for the non
specialist. However, many references are provided, and tables of
most of the known compounds and their properties are included in
the appropriate chapters. The reader will find comprehensive
reviews of publications in Friends Textbook of Inorganic Chemistry,
Volume 11, Part 2 Krause and von Grossed Chemie der
Metallorgamschen Ver bindungen, Dolgows Chemistry of the
Silica-Organic Compounds, and Bygdens Silizium als Vertreter des
Kohlenstoffs organischen Verbindun gen. A more recent and more
complete compilation of the literature on organic compounds of
silicon would be welcomed by every investigator in the field. Since
this work presents a point of view rather than an uncritical
compilation of published fact, the author must assume entire
responsi bility for the opinions expressed. However, he is greatly
indebted to his coworkers iu the research laboratory of the General
Electriq Com vii viii PREFACE pany for helpful advice and
criticisms. In a larger sense this work is the result of many years
of common endeavor in a most interesting field of research.
CONTENTS CHAPTER PAGE 1. THE SIMPLE COVALENT COMPOUNDS OF SILICON 1
Introduction 1 Chemical Behavior of the Element 3 The Hydrides 4
The Halides 9 The Esters or Ethers 12 Index of Representative
Compounds 16 2. THE ORGANOSILICON MONOMERS 18 Methods for
Carbon-Silicon Bonds 19 The Alkyls 30 The Alkylsilanes 32 The
Alkylhalosilanes 33 The Alkylalkoxysilanes 37 Index of
Representative Compounds 39 3. TYPES OF ORGANOSI LICON POLYMERS 45
Silicon Chains 45 Silicon-Carbon Chains 46 Siloxane Chains
49Siloxane Networks 53 Index of Representative Compounds 58 4.
PROPERTIES OF THE SPECIFIC SILICONS POLYMERS 60 Alkyl Silicones 62
Methyl Silicone Oil 64 Methyl Silicone Resins 70 Silicone Rubber 72
Ethyl Silicone Resins 73 Other Alkyl Silicone Resins 74 Aryl
Silicones 77 Alkyl-Aryl Silicones 80 5. WATER-REPELLENT FILMS FROM
ORGANOSILICON MATERIALS 83 Reaction of Methylchlorosilanes 83 Uses
85 6. TECHNICAL ASPECTS OF SILICONES 89 The Intermediates 90 The
Grignard Method 91 The Direct Method 96 Processing 101 Toxicity 103
Future Expansion 104 ix CONTENTS CHAPTER 7...
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