Coordination Polymerization. A Memorial to Karl Ziegler

352 Pages·1975·5.725 MB·English

by  James C.W. Chien (Eds.)

Academic Press Rapid Manuscript Reproduction
COORDINATION
POLYMERIZATION
A Memorial to Karl Ziegler
Edited by
JAMES C.W. CHIEN
Department of Chemistry
Department of Polymer Science and Engineering
Polymer Research Institute
Material Research Laboratories
University of Massachusetts
Amherst, Massachusetts
Academic PreSS, InC. New York San Francisco London 1975
A Subsidiary of Harcourt Brace Jovanovich, Publishers
COPYRIGHT © 1975, BY ACADEMIC PRESS, INC.
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ACADEMIC PRESS, INC.
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United Kingdom Edition published by
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Library of Congress Cataloging in Publication Data
Main entry under title:
Coordination polymerization.
Proceedings of a symposium sponsored by the American
Chemical Society and held April 3, 1974, at UCLA.
Includes bibliographies and index.
1. Polymers and polymerization-Congresses.
2. Coordination compounds-Congresses. 3. Ziegler,
Karl Waldemar, (date) —Congresses. I. Ziegler,
Karl Waldemar, (date) II. Chien, James C. W.,
(date) III. American Chemical Society.
QD380.C66 547'.28 75-33101
ISBN 0-12-172450-6
PRINTED IN THE UNITED STATES OF AMERICA
KARL ZIEGLER
List of Contributors
D.G.H. Ballard, ICI Corporate Laboratory, The Heath, Runcorn, Cheshire,
England
C. Carlini, Istituto di Chimia Organica Industriale, Universite di Pisa, 35, via
Risorgimento, 56100 Pisa, Italy
E. Chiellini, Istituto di Chimia Organica Industriale, Universite de Pisa, 35, via
Risorgimento, 56100 Pisa, Italy
J.C.W. Chien, Department of Chemistry, Department of Polymer Science and
Engineering, Materials Research Laboratory, University of Massachusetts,
Amherst, Massachusetts 01002
F. Ciardelli, Istituto di Chimia Organica Industriale, Universite di Pisa, 35, via
Risorgimento, 56100 Pisa, Italy
F.S. Dyachovskü, Institute of Chemical Physics, Academy of Science USSR,
Cherrogolovka, Norginsk District, Moscow 142432, U.S.S.R.
S. Fuji, Research Center, Mitsui Petrochemical Industries, Ltd., Waki-Mura,
Kuga-Gun, Yamaguchi-Ken, 740, Japan
G. Henrici-Olivé, Monsanto Research S. Α., Eggbühl-Strass 36 CH-8050
Zürich, Switzerland
/. T. T. Hsieh, Department of Chemistry, Department of Polymer Science and
Engineering, Materials Research Laboratory, University of Massachusetts,
Amherst, Massachusetts 01002
M. Julemont, Laboratoire de Chimie Macromoléculaire et de Catalyse Organique,
Université de Liège, Sart-Tilman, 4000 Liège, Belgium
ΚΑ. Jung, Department of Chemistry, University of Mainz, 65 Mainz, G.F.R.
T. Keii, Department of Chemical Engineering, Tokyo Institute of Technology,
Meguro, Tokyo, Japan
W. Kern, Department of Chemistry, University of Mainz, 65 Mainz, G.F.R.
ix
LIST OF CONTRIBUTORS
S. Olive, Monsanto Research S. Α. ,Eggbühl-Strasse 36 CH-8050 Zürich,
Switzerland
Α. Oschwald, Eidgenössische Technische Hochschule Zürich, Universität-
strasse 6, CH-8006 Zürich, Switzerland
P. Pino, Eidgenössische Technische Hochschule Zürich, Universität-strass 6,
CH8006 Zürich, Switzerland
H. Schenecko, Dunlop-Forschungslaboratorium, 645 Hanau, Postfach 129
G.F.R.
PJ.T. Tait, Department of Chemistry, University of Manchester Institute of
Science and Technology, Manchester M61 1QD, England
Ph. Teyssié, Laboratoire de Chimie Macromoléculaire et de Catalyse Organique,
Université de Liège, Sart-Tilman, 4000 Liège, Belgium
JM. Thomassin, Laboratoire de Chimie Macromoléculaire et de Catalyse
Organique, Université de Liège, Sart-Tilman, 4000 Liège, Belgium
Ε. Walckiers, Laboratoire de Chimie Macromoléculaire et de Catalyse Organique,
Université de Liège, Sart-Tilman, 4000 Liège, Belgium
R. Warin, Laboratoire de Chimie Macromoléculaire et de Catalyse Organique,
Université de Liège, Belgium
G. Wilke, Max-Planck-Institut fur Kohlenforschung, 433 Mülheim A. D .Ruhr,
Kaiser-Wilheim-Platz, G.F.R.
Yu. I. Yermakov, Institute of Catalysis, 630090 Novosibirsk,! U.S.S.R.
V.A. Zakharov, Institute of Catalysis, 630090 Novosibirsk, U.S.S.R.
A. Zambelli, Instituto di Chimicadelle Macromolecole,; via Alfonso Corti N. 12,
20133 Milano, Italy
χ
PREFACE
It was exactly 20 years ago that Ziegler discovered the catalyst system that
made it possible to polymerize ethylene at low pressure to linear high density
polyethylene. Subsequently Natta developed catalyst systems for stereospecific
polymerizations of α-olefins. Soon it was realized that the mechanism of these
polymerizations is distinctly different from others and that the propagating
chain is coordinated to the catalyst. The principle of coordination polymeriza-
tion has been applied successfully to other monomers. The Polymer Chemistry
Division asked M. Tsutsui and myself to organize a symposium to look at what
lies ahead for coodination polymerization.
While we were organizing this symposium, the news of the death of Professor
Ziegler shocked the scientific community. The organizers proposed to the Poly-
mer Chemistry Division and received unanimous approval to make the sym-
posium a memorial to K. Ziegler. We were able to bring together for the
occasion many scientists who are major contributors to the field of Ziegler-
Natta catalysis. Because of the limitation of time it was possible to accom-
modate only a limited number of speakers. Other scientists were invited to
contribute additional papers. This book contains all these contributions.
In Chapter 1, Wilke, who succeeded Ziegler as Director of the Max-Planck-
Institut für Kohlenforschung, traces Ziegler's various major contributions tc
the chemistry of free radicals, organo-alkali metal compounds, many membered
rings and organotransition metallic compounds.
In Chapters 2 and 3 the origin of steric control in the polymerization of
α-olefîns is discussed. In particular the elegant work of Pino and colleagues
on steroselection and stereoelection shows that it is the chirality of the transi-
tion metal which dictates the stereoregularity of the polymer produced.
The counting of active sites has been a problem o fcentral importance to the
mechanism and kinetics of coordination polymerizations. Chapters 4-7 deal
with this problem in depth and show comparisons of results obtained with
various methods. These chapters are particularly useful because the limitations
in each method are clearly spelled out for the benefit of others who migh twish
to employ the techniques. With the concentrations of active sites thus de-
termined, some absolute rate constants are presented in these chapters.
xi
PREFACE
To elucidate the mechanisms of initiation, propagation, termination and
transfers. Chapter 8 deals with polymerizations by (TT-C H ) TiCl catalysts.
5 5 2 2
Chapter 9 describes the polymerizations by allyl, benzyl, trimethylsilmethy 1
and other derivatives of Ti and Zr. The kinetics of Ziegler-Natta polymerization
is treated, along with the Langmuir adsorption mechanism, in Chapter 10.
The real new areas of Ziegler-Natta polymerizations are discussed in the last
two chapters. In Chapter 12 results of supported catalysts are presented. The
factors influencing the stereoregularity of polymerization of propylene by sup-
ported catalysts are investigated and delineated. Results of ethylene poly-
merizations by supported catalyst are also contained in Chapters 5 and 9. In
Chapter 13 the interesting polymerizations of diolefîns to equibinary polymers
3
by h -allylic coordination complexes are discussed.
The organizers wish to acknowledge financial contributions from Dow Chem-
icals, Ε. I. duPont de Nemours & Co., Witco Chemical Corporation,Farbwerke
Hoechst AG, and the Polymer and Science Engineering Department of the
University of Massachusetts. These funds made it possible to bring the foreign
scientists to the Symposium.
Finally, Frau Maria Ziegler was kind enough to send us her favorite photo of
Professor Ziegler for this memorial publication. The editor is also grateful to
the National Science Foundation for support through grant GH-39111.
James C. W. Chien
xii
Karl Ziegler, in Memoriam
G. WILKE
Max-Planek-Institut für Kohlenforschung
Mülheim a.d* Ruhr
Germany
KARL ZIEGLER DIED IN MÜLHEIM A.D. RUHR ON THE LLTH
AUGUST 1973 SHORTLY BEFORE HIS 75TH "BIRTHDAY. A WEEK LATER
WE HEARD THAT THE ACS HAD DECIDED TO HOLD A MEMORIAL SYMPO-
SIUM IN HIS HONOR AS PART OF THE SPRING MEETING IN LOS
ANGELESο THE NEWS OF THIS DECISION COMING AS IT DID SO SOON
AFTER HIS DEATH MADE A GREAT IMPRESSION UPON FRAU ZIEGLER AND
THE CLOSE FRIENDS AND RELATIVES AND FRAU ZIEGLER HAS ASKED ME
TO CONVEY HER THANKS TO THE ORGANIZERS OF THE ACS FOR THIS
GESTUREο
REMARKABLE IN KARL ZIEGLER 1S CAREER IS THE EARLY DATE AT
WHICH HE STARTED IN THE DIRECTION WHICH MANY YEARS LATER WAS
TO BE CROWNED WITH SUCH CONSIDERABLE SUCCESS. ZIEGLER WAS
BORN ON THE 26TH NOVEMBER 1898 IN HELSA NEAR KASSEL THE
SON OF A MINISTER (WHO HAD STUDIED THEOLOGY AT THE UNIVERSITY
OF MARBURG) AND HIS INTEREST IN CHEMISTRY STEMS FROM A HOME-
LABORATORY IN WHICH HE WAS WORKING ALREADY AT THE AGE OF
ELEVEN. BY THE TIME HE WENT TO THE UNIVERSITY OF MARBURG TO
STUDY CHEMISTRY; HE HAD OBTAINED SUCH A WIDE KNOWLEDGE THAT
AFTER THREE OR FOUR WEEKS HE WAS ALLOWED TO TRANSFER DIRECTLY
TO THE THIRD SEMESTER. FOR THIS REASON IT IS NOT SURPRISING
THAT HE RECEIVED HIS DOCTORAL DEGREE SHORTLY BEFORE HIS 22ND
BIRTHDAY. HIS DOKTORVATER WAS KARL VON AUWERS WHO VERY SOON
ENCOURAGED HIM TO MAKE HIMSELF INDEPENDENT. ZIEGLER MARRIED
IN 1922 AND SUBMITTED HIS "HABILITATIONS" THESIS IN 1923.
THIS THESIS CONTAINED THE FIRST STUDIES OF THE ADDITION OF A
METAL-CARBON BOND TO A C»C DOUBLE BOND WHICH WAS LATER TO
BECOME SUCH AN IMPORTANT AND VERSATILE REACTION. I WILL
RETURN TO THIS POINT LATER BUT FIRST WE WILL FOLLOW ZIEGLER
IN THE FURTHER DEVELOPMENT OF HIS CAREER.
IN 1925-1926 HE LECTURED AT THE UNIVERSITY OF FRANKFURT
AND IN 1926 HE JOINED KARL FREUDENBERG AT HEIDELBERG.
WILLSTATTER1S PROPHECY THAT HE WOULDN'T STAY LONG IN HEIDEL-
BERG PROVED TO BE FALSE: ZIEGLER SHOWED A MARKED ANTIPATHY
1
G. WILKE
TO THE POLITICAL DEVELOPMENTS WHICH WERE SOON TO APPEAR AND
IN SPITE OF THE ECONOMIC CRISIS AND POLITICAL CLIMATE HE
SPENT TEN HAPPY YEARS AT HEIDELBERG. IN THIS TIME THE THREE
AREAS WHICH WERE TO ATTRACT HIS MAIN INTEREST TOOK SHAPE. IT
WAS SOON NO LONGER POSSIBLE TO IGNORE ZIEGLER'S SCIENTIFIC
ACHIEVEMENTS AND IN SPITE OF HIS POLITICAL OPINIONS HE WAS
OFFERED THE CHAIR OF CHEMISTRY AT THE UNIVERSITY OF HALLE IN
1936 WHERE HE BECAME DIRECTOR OF THE HALLE INSTITUTE. IN
I9I+3 HE WAS OFFERED THE DIRECTORSHIP OF THE KAISER-WILHELM-
INSTITUT FÜR KOHLENFORSCHUNG IN MÜLHEIM A.D. RUHR. ZIEGLER'S
INITIAL REACTION WAS NEGATIVE SINCE HE COULD SEE NO CONNEC-
TION BETWEEN HIS INTERESTS AND THAT OF COAL RESEARCH.
HOWEVER, THE BOARD OF DIRECTORS SHOWED CONSIDERABLE FORESIGHT
AND ALLOWED HIM TO CHOOSE HIS OWN RESEARCH AREA. HIS INTER-
PRETATION OF COAL RESEARCH AS BEING THE INVESTIGATION OF THE
CARBON-COMPOUNDS IN ITS WIDEST SENSE DID NOT ALWAYS MEET WITH
THE FULL APPROVAL OF THE FINANCING PARTIES IN THE RUHRGEBIET
BUT THE CRITICAL VOICES WERE SILENCED AFTER THE DEVELOPMENTS
OF 1952.
I HAVE MENTIONED THAT ZIEGLER WAS ENGAGED MAINLY IN
THREE RESEARCH FIELDS: TWO OF THESE, "ZUR KENNTNIS DES
'DREIWERTIGEN1 KOHLENSTOFFS" (CONCERNING THREE-VALENT CARBON)
AND "UNTERSUCHUNGEN ÜBER ALKALIORGANISCHE VERBINDUNGEN (CON-
CERNING THE ORGANOALKALIMETAL COMPOUNDS), HAVE THEIR ORIGIN
IN HIS "HABILITATIONS" THESIS WHILE THE THIRD, "UBER VIEL-
GLIEDRIGE RINGE" (CONCERNING MANY MEMBERED RINGS) WAS
DEVELOPED IN THE THIRTIES. THE SECOND THEME WAS LATER
GENERALIZED TO "METALLORGANISCHE VERBINDUNGEN" (CONCERNING
ORGANOMETALLIE COMPOUNDS). IN THE FOLLOWING I SHALL BRIEFLY
DISCUSS EACH OF THESE TOPICS.
THREE-VALENT CARBON
IN 1923 ZIEGLER WROTE: "THE FOLLOWING IS INTENDED TO BE
THE FIRST OF A NUMBER OF PUBLICATIONS IN WHICH AN ATTEMPT IS
MADE TO IDENTIFY THE FACTORS RESPONSIBLE FOR THE DISSOCIATION
OF SUBSTITUTED ETHANE DERIVATIVES". ZIEGLER'S CONCERN WITH
THIS PROBLEM DURING THE YEARS BETWEEN 1923 AND 1950 RESULTED
IN MANY PUBLICATIONS. BY SYSTEMATIC ALTERATION OF THE SUB-
STITUENT S IN HEXA-SUBSTITUTED ETHANE DERIVATIVES E.G., THE
REPLACEMENT OF AN UNSATURATED GROUP BY A SATURATED ONE,
INFORMATIONS WERE OBTAINED ON THE ROLE OF STERIC AND ELEC-
TRONIC FACTORS IN THE DISSOCIATION PROCESS. A METHOD
DEVELOPED BY ZIEGLER AND SCHNELL - THE SO-CALLED ETHER-METHOD
- ENABLED THE SUBSTITUENTS TO BE WIDELY VARIED.
2