From organic chemistry to macromolecules : A scientific autobiography based on my original papers

290 Pages·1970·8.999 MB·English

by  Hermann Staudinger

Hermann Staudinger

From Organic Chemistry
to Macromolecules

A scientific autobiography
based on my original papers

TRANSLATED FROM THE GERMAN

With a Foreword by

HERMAN F. MARK

109917

Wiley-Interscience

a Division of John Wiley & Sons, Inc.

New York London Sydney Toronto
Translated from Hermann Staudinger, Arbeitserinnerungen,
© 1961, Dr. Alfred Hiithig Verlag GmbH, Heidelberg,
by Jerome Fock and Michael Fried

Copyright © 1970, by John Wiley & Sons, Inc.

All rights reserved. No part of this book may be reproduced
by any means, nor transmitted, nor translated into a machine
language without the written permission of the publisher.

Library of Congress Catalogue Card Number: 67-21664
SBN 471 82086 5
Printed in the United States of America
10 9 8 7 6 5 4 3 2 1
To my dear wife Magda

THE INSPIRING AND UNTIRING COLLABORATOR
IN THE FIELD OF MACROMOLECULES
in gratitude
Foreword

Thirty years ago, there appeared a volume containing the papers
published by W. H. Carothers, the great American pioneer in polymer
science, as a result of ten years of intense research together with some ten
able co-workers in the Experimental Station of the Du Pont Company
in Wilmington, Delaware. A similar book should have appeared at the
same time containing the collected papers of the great European pioneer
of this field, Hermann Staudinger, covering his work over twenty years
with some fifty students and associates. It did not appear. War emergencies,
postwar needs, and urgent pressure to rebuild the Institute prevented
Staudinger's pausing to take stock of his life's work. Finally, in 1961 the
German edition of Arbeitserinnerungen was published. Now, another
ten years later, we have in our hands an English version of the account of
his work. It is fifty years after the first paper was printed and ten years after
the last was published; this is a long span. But monuments do not lose
their appeal with time; in fact, as they grow older, they become even more
venerable. We can savor opening this book and reading, in the master's own
words, about how the concept slowly emerged from the haze of conflicting
opinions, how interest and intensity gradually increased, and how by the
tortuous path of trial and error clarification was finally reached in a step-
by-step approximation.
Every page breathes the air of firsthand authenticity; we have entered
the laboratory with its odor of styrene and formaldehyde, its glittering
glassware, and its slowly agitated thermostats. We can see the Professor
surrounded by his students as he explains to them how they should con-
duct their experiments, register their data, draw their conclusions, appraise
their significance, and assist him in weaving the complex fabric of macro-
molecular chemistry.

Vll
viii FOREWORD

Carothers in ten tense years of his short life enriched the world with an
impressive list of extremely useful polymers, which not only established his
and his associates' reputation in the forefront of the art but also produced,
in the hands of congenial engineers, an enormous dividend for his
company and convenience, pleasure, and safety for millions of people.
Staudinger in fifty years of his long life created a galaxy of distinguished
polymer chemists, many of whom reached leading positions in universities
and in industrial organizations and ultimately had a very similar impact on
the science and technology of the art.
In the clarified atmosphere of hindsight it becomes evident that Staudin-
ger's impact on his time was caused by a triple role which he kept on
playing with never-failing enthusiasm for more than forty years-as
explorer, teacher, and preacher. Guided by true scientific curiosity for the
unknown, Staudinger selected as the work of his life in the early 1920's a
field which, at that time, was hardly considered to be a worthy goal for an
organic chemist of his reputation-the study of the natural organic sub-
stances of high molecular weight. Until then, Staudinger had cultivated
typical problems of classical organic chemistry with its well-defined
substances which could be characterized by such methods as melting and
boiling point, freezing point depression, and boiling point elevation. A
stimulating monograph, The Chemistry of the Ketenes, was the fruit of
these efforts, a book that seemed to foreshadow Staudinger's career as
that of a synthetic organic chemist worthy of such great predecessors as
Baeyer, Fischer, and Gattermann and of such distinguished contemporaries
as Schlenk and WillsHitter.
However, he chose the more romantic, though less comfortable, life of
an invader of unknown areas, where every step would have to be a fight
for new concepts, new methods, and new interpretations. In this area of
the natural and synthetic substances of high molecular weight he performed
first of all the miraculous task of carrying out, with the help of his numerous
collaborators, many thousands of individual experiments on materials
varying from natural substances, like starch, cellulose, and rubber, to syn-
thetic materials, such as polystyrene and polyamides, and applying purely
organic methods, such as hydrogenation, nitration, and end group deter-
mination, with the same systematic persistence as he applied such physical
measurements as osmotic pressure and viscosity determinations. Through
this work Staudinger ranks first in having introduced the new branch of
macromolecular chemistry with the largest number of facts and figures,
both by observation and by measurement.
The second great achievement of the author of our book was his success
.

FOREWORD
IX

in transmitting the spirit of adventurous thinking, combined with sober
experimental reliability, to a large number of students, who sat at the
master's feet and could not fail to become thoroughly persuaded that his
macromolecular chemistry was a strong and big branch on the tree of sci-
ence, destined to grow just as fast and irresistibly as macromolecules them-
selves. Together with this idea, however, they carried into their positions in
academic and industrial life also the deep conviction that the growth of
polymer chemistry would depend entirely on meticulous and careful
experimentation with m thods newly designed and developed for this
field. A generation of leaders in high schools, universities, and industrial
laboratories emerged from Zurich and Freiburg, the "Highboroughs of
High Polymers."
The third and, indeed, not the least important role that Staudinger
had to assume as his work progressed was that of an apostle. Many of his
colleagues in high academic positions remained for a long time skeptical
and overcautious. They did not approve of the strong terms with which
Staudinger elevated his own working field to a "new branch of organic
chemistry," and they displayed mistrust in a number of his methods and
results. It was this atmosphere of negative incredulity that Staudinger
combated throughout the years without fatigue and impatience. Again and
again-in conferences, symposia, and conventions-he stood up as chair-
man, lecturer, or discussion speaker. He developed his ideas, explained the
coherent pattern of the new concepts, and defended his position against all
attacks with his native ingenuity and enthusiasm.
There exist numerous, unforgettable occasions, in the 1920's and 1930's,
when history of chemistry was made in the eloquent clashes between
Staudinger and the representatives of the "aggregation theory of the small
units." Holding firm to his main ideas and introducing modifications
wherever the facts demanded them, Staudinger emerged from these battles
as the grand old man of macromolecular chemistry, the Nobel Prize
winner, the honorary doctor of many institutions of higher learning, the
fatherly friend to his pupils, and the benevolent counce! of his colleagues.
High ideals, creative imagination, and hard work were never more
splendidly and more deservedly rewarded than in the case of the man whose
life's work is now finally in our hands. All readers of this volume will be
grateful to him for giving it to us and to his wife for patiently and faithfully
insisting on the publication of this English version.

F.
HERMAN MARK

Polytechnic Institute of Brooklyn
Apri/1970
Preface to the English Edition

Shortly after my husband's Arbeitserinnerungen appeared in 1961, the
translation of this book into English was suggested, and my husband was
very pleased when John Wiley & Sons, Inc.-Interscience Publishers took
on the task in 1962.
Unfortunately, my husband passed away before the completion of the
translation, which is presented now. It is a literal rendition of the original,
because it is a "biography of work" and thus a kind of historical review
of the exciting beginnings of macromolecular chemistry, which has now
attained an enormous volume both in research and in industry.
My best thanks are due to Professor Dr. Heinrich Hopfffor his assistance
in the translation, and to Professor Dr. Hermann F. Mark for his offer to
write a foreword. I also owe many thanks to the publishers for their
interest and the help given in producing the book.
In looking through the proofs of this last book of my husband's I
feel deep gratitude for having been able to share in the development of his
macromolecular science.

MAGDA STAUDINGER

Freiburg i.Br.
May 1970

X
Preface to the German Edition

Several years ago it was suggested that I publish a complete collection
of my scientific papers. This plan was soon discarded because the book
would have become much too large. Instead, we compiled a catalog of all
my scientific papers, grouping them according to subject areas, to achieve
a better overview of the more than 800 publications within the different
branches of chemistry. This task was accomplished a few years ago by two
of my collaborators, Dr. Walter Hahn and Dr. Helmut Ringsdorf, to whom
I wish to express my appreciation.
Subsequently, we added to this listing, during recent years, introductory
notes to explain the historical development which led to the publication of
these papers.
Since I have been asked repeatedly about the considerations which led
me to the development of the concept of macromolecules, I described these
in greater detail. In doing so, I surveyed the development of macro-
molecular chemistry during the past decades.
The resulting manuscript has been carefully examined by Dr. Gunther
Welzel, for which I extend my warmest thanks to him.
The several drafts necessary for the completion of the present book were
prepared with great care by Mrs. H. Rossmy. As my secretary for many
years, she helped me also in the transcribing of all other papers and books
in the last decade, for which I express my deepest appreciation.
This book is published by Dr. Alfred Hiithig Verlag, the publisher of
the journal, Die Makromolekulare Chemie, which I founded and was the
editor for more than ten years. I express my gratitude to Dr. Alfred
Hiithig for the care he took in publishing this book.
Only through the joint effort of many collaborators was it possible to
accomplish the scientific work of which the papers treated in this book are

XI
xii PREFACE TO THE GERMAN EDITION

the result. To these many collaborators I would like again, on this occasion,
to express my gratitude.
At the same time, I gratefully acknowledge the assistance which I
received for the execution of this research from financial grants and for
counsel and advice.
I am presenting these Arbeitserinnerungen in the hope that they will be
useful to the chemist of today and that the present-day investigators of
macromolecules will receive stimulation from them by becoming acquainted
again with the historical development of this field.
H.
STAUDINGER

Freiburg i.Br.
March 1961
Contents

..

Foreword by Herman F. Mark .
Vll

Preface to the English Edition
X

Preface to the German Edition
XI
Introduction 1
PART A. RESEARCH ON LOW MOLECULAR COMPOUNDS
AND PUBLICATIONS ON GENERAL SUBJECTS
1. The Ketenes. I 1
.
2. Aliphatic Diazo Compounds 18
3. New Organic Phosphorus Compounds 24
4. Reactions of Methylene . 28
5. Autoxidation of Organic Compounds 31
6. Oxalyl Chloride 36
7. Explosions . 39
8. Synthesis of Isoprene 43
9. Insecticides . 46
10. Synthetic Pepper 49
Xlll