Olefin Metathesis and Polymerization Catalysts: Synthesis, Mechanism and Utilization

566 Pages·1990·24.15 MB·English

by  K. J. Ivin (auth.)

Oletin Metathesis and Polymerization Catalysts
NATO ASI Series
Advanced Science Institutes Series
A Seri es presenting the results of activities sponsored by the NA TO Science Committee,
which aims at the dissemination of advanced scientific and technological knowledge,
with a view to strengthening links between scientific communities.
The Series is published by an international board of publishers in conjunction with the
NATD Scientific Affairs Division
A Life Sciences Plenum Publishing Corporation
B Physics London and New York
C Mathematical Kluwer Academic Publishers
and Physical Sciences Dordrecht, Boston and London
D Behavioural and Social Sciences
E Applied Sciences
F Computer and Systems Sciences Springer-Verlag
G Ecological Sciences Berlin, Heidelberg, New York, London,
H Cell Biology Paris and Tokyo
Series C: Mathematical and Physical Sciences -Voi. 326
Oletin Metathesis
and Polymerization Catalysts
Synthesis, Mechanism and Utilization
edited by
Yavuz imamoglu
Department of Chemistry,
Hacettepe University, Ankara, Turkey
BirgOl ZOmreoglu-Karan
Department of Chemistry,
Hacettepe University, Ankara, Turkey
and
Alian J. Amass
Department of Chemical Engineering and Applied Chemistry,
Aston University, Birmingham, U.K.
Springer Science+Business Media, B.V.
Proceedings of the NATO Advanced Study Institute on
Olefin Metathesis and Polymerization Catalysts
Akcay, Turkey
September 10-22, 1989
Library of Congress Cataloging-in-PublicaUon Data
NATD Advanced Study Institute on Dlefin Metathesis and Polymerizatlon
Catalysts: Synthesis. Mechanism. and Utilization (1989 Ak,ay.
Turkeyl
Dlefin metathesis and polymerization catalysts : synthesis.
mechanism. and uti I ization : proceedlngs of the NATD Advanced Study
Institute on Dlefln Metathesis and Polymerization Catalysts
-Synthesis. Mechanism. and Utilization. Ak,ay. Turkey. September
10-22. 1989 / edited by Yavu2 imamoglu, Birgu1 Zumreoglu-Karan, and
AI1an J. Amass.
p. cm. -- (NATO ASI ser ies. Series C, Mathematical and
physical sciences ; val. 3261
Includes index.
ISBN 978-94-010-5470-6 ISBN 978-94-011-3328-9 (eBook)
DOI 10.1007/978-94-011-3328-9
1. Catalysis--Congresses. 2. Alkenes--Congresses. 3. Metathesis
(Chemlstryl--Congresses. 4. Polyrnerization--Congresses.
1. imamog I u. Yavuz. 1945- II. Zumreoglu-Karan, Birgul, 1955-
III. Amass. Alian J .• 1943- IV. Title. V. Ser ies: NATD ASI
series. Series C, Mathematical and physical sciences ; no. 326.
OD505.N365 1989
660' .2995--dc20 90-20345
ISBN 978-94-010-5470-6
Printed on acid-free paper
AII Rights Reserved
© 1990 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 1990
Softcover reprint of the hardcover 1s t edition 1990
No part of the material protected by this copyright notice may be reproduced or
utilized in any form or by any means, electronic or mechanical, including photo
copying, recording or by any information storage and retrieval system, without written
permission from the copyright owner.
TABLE OF CONTENTS
PREFACE 1X
List of Participants xi
OVERTURE: Olefin Metathesis and Metathesis Polymerization , A Historical 1
Perspective
K.J. Ivin, UK
PART 1. HOMOGENEOUS SYSTEMS
The Stereochemistry of Metathesis of Acyclic and Cyclic Olefins 45
J-M. Basset .... D. Boutarfa, E. Custodero, M. Leconte and C. Palliet
Electrochemical Generation of Catalysts for Alkene Metathesis 89
S. Bages, M. Petit, A. Mortreux and F. Petit'"
Catalysts for the Hom.ogeneous Metathesis of Functionalized Ole fins 115
J,C. Mol
Block Copolym.ers by Anionic to Metathesis Transformation Reactions lil
A.J. Amass" . D. Gregory, B.J. Tighe and M.A. Tyler
The Kinetics of Polymerization of Cyclopentene 167
A.J. Amass". M. Lotfipur, B.]. Tighe. C.N. Tuck and lA. Zurimendi
Tacticity in Polymers Initiated by Metathesis Polymerization: Effect of 187
Catalyst
K.J.Ivin
Degradation of Polymers by Metathesis Catalysts 209
K. Hummel
vi
Metathesis Polymerization by Homogeneous Catalysts: Simulations
L. Bencle
PART II. HETEROGENEOUS SYSTEMS
General Properties of Supported Metathesis Catalysts 24i
JC Mol
Surface Funclionalization of Supported Catalysts "''''1
/.Ii
K,Tanaka
Novel Supported Catalysts for Terminal Alkene Metathesis 303
K,Tanaka
Characterisation of Rhenium Oxide! Alumina MetathesiS Catalysts
A. Ellison
Stoichiometric Reactions with Reduced Phillips Catalysts 359
H.L. Krauss"'. E. Amberger, N. Arfsten, P. BlOme!. W. Hammon,
R. Hopfl and W. Riederer
Catalytic Reactions with Reduced Phillips Catalysts 373
HL Krauss". B. Frank. B. Hanke, E. Hums, D. Langstein,
D. Naumann, B, Siebenhaar and K. Weiss
Non-Chromium Surface Compounds 383
HLKrauss*, G Guldner, M. Hornscheldt, N, Larsen, R. Merkel.
P. Morys, S. Schmerbeck and P. Zahn
Coordination Chemistry of Silica Supported Cr Ions: 393
Types of CrUn Ions on Reduced Samples
E, Garrone*, G. Ghiotti and A. Zecchina
vii
Structural Analysis of Supported Chromium Systems 407
A. Ellison
PART III, INDUSTRIAL ASPECTS
Induslrial Aspects of Olefin Metathesis I Polymerization Catalysts
R Streck
1. Historical Development 439
2, Present Industrial Status and Outlook 457
3. Technological Properties and Applications of Metathesis Polymers 489
PART IV. SHORT CONTRIBUTIONS
1. Papers
Syntheses of Heterogeneous. Bimetallic Metathesis Catalysts by Reactions 517
of FIscher Type Carbene and Carbyne Complexes with Reduced PhilliPS Catalyst
K. Weiss*, W. Guthmann, M. Denzner and S. Maisuls
New Results on Alkene Metathesis and Alkyne Polymerisation with )21
Heterogeneous Carbene Tungsten(VI:l Complexes
K,Weiss"', G. Ll:lssel and M, Denzner
Aqueous Ring-Opening Metathesis Polymerizations of 7-0xa-norbornene 323
Derivat1ves Usmg Ruthenium Catalysts
D,V. McGrath"', B.M. Novak. and R.H, Grubbs
The Application of Ring Opening Metathesis Polymerization to ~he 337
Synthesis of Substituted Polyacetylenes
E.j. Ginsburg*. C.B, Gorman, M.J. Sailor, N.S. Lewis and R.H. Grubbs
2. Posters (Abs~racts)
Raman Spectroscopy of Surface Rhenium Oxide on Alumma. Silica,
Titania, Niobia and Magnesia
f.D. Hardcastle" ,Jih-Mirn Jehng, Chung-Ku Chen and I.E. Wachs
viii
Raman Spectroscopy of Chromium Oxide Supported on Alumina, Titania 545
and Silica: A Comparative Study
F.D. Hardcastle" and I.E. Wachs
Stoichiometric and Catalytic Carbene Complex Reactions with the 537
Reduced Phillips Catalyst
f.. Weiss
Metathesis-Like Reactions of Heteroalkenes and Het.eroallenes 549
with the Ca.rbyne Complex C13(dme)W=CCMe3
K. Weiss* and R. Goller
Catalytic Metathesis of Alkynes )51
S.Bages. M.Petit*. A. Mortreaux and F. Petit
Electrochemical Synthesis of Catalytic Spedes for Alkene Metathesis 553
S. Bages*, M.Petit, A. Mortreaux and F. Petit
Chromium Supported Catalysts for Ethylene Gas Phase Polymerization 5'55
JR.G. Velasco", M.A.G. Ortiz. JI.G. Ortiz. J.A.G. Marcos and j.I.A. Uriarte
»7
Metathetical Degradation of Sulfur Vulcanized Polybutadiene
by W(CO)6/ eC14 I hv
C. Bozkurt* and Y. Imamoglu
Photocatalytic Ring-Opening Polymerization of Norbornene and 5)9
Norbornadiene and Cyc10pentene
B. DOz*. C. Bozkurt and Y. Imamoglu
PART V. RESEARCH PROSPECTS 561
INDEX 565
PREFACE
Olefin metathesis reaction can be considered as one of the most successful organic
reactions with many applications in the low molecular weight range and also in the
polymer field. The use of catalysts with their selective and effective transformation
properties in olefin metathesis I polymerization systems is a growing interest. There has
been great effort and competition in developing active and commercially useful catalysts.
The main aim of this ASI was to gather several research groups and also the people
from industry. to present existing knowledge and latest results in the field. A wide range
of topics through homogeneous and heterogeneous aspects have been considered.
Attention has been drawn to the metal-carbene and metallacyclobutane complexes as
active species, the initiation mechanisms, the stereochemistry and thermodynamics of
these reactions. New catalytic systems for the metathesis of alkenes and alkynes and fot'
ring opening polymeriZation I block copolymerization reactions have been introduced.
Spectroscopic studies for the characteriZation of catalysts, simulation studies explaining
the function of chain carrier species and polymer degradation have also been covered. A
detailed industrial report concerning the patents and applications in olefin metathesis I
cyc1001efin polymerization area, fabrication and derivation has been presented.
This volume contains the main lectures and seminars given at the NATO Advanced
Study Institute on " Olefin Metathesis and Polymerization Catalysts: Synthesis, Mechanism
and Utilization", held at Akcay. Babkesir. Turkey between 10th and 22nd September 1989.
In addition to about 2llectures a further four short contributions and poster abstracts are
also included. Finally, the issue of research prospects is discussed. The volume is addressed
to the research workers in the area of metathesis I polymerization systems as well as to
those who are utilizing them or it could serve as a textbook for advanced courses.
The Institute was generously sponsored by the Scientific Affairs Division of NATO and
the editors gratefully acknowledge for this sponsorship. We also express our gratitude to
a.ll of the speakers and participants who contributed the success of the Institute. Finally,
we would like to thank the members of the local organizing committee for their effort in
creating a pleasant atmosphere during the Institute.
YA VUZ IMAMOGLU , BIRGUL ZUMREOGLU-KARAN and ALLAN J AMASS
August. .1990
ix
LIST OF PARTICIPANTS
MahirALKAN Department of Chemistry
KSZim Karabeldr Education Faculty
AtatOrk University. ERZURUM (Turkey)
Allan J. AMASS Department of Chemical Engineering and
Applied Chemistry
Aston University
GostaGreen. BIRMINGHAM B47IT <UK)
Elisabeth AMBERGER Laboratorium fOr Anorganische Chemie
Universitaet Bayreuth
Postfach 10 1251, 8580 BAYREUTH (Germany)
Sylvie BAGES Ecole National Superior de Chimie
BP 108.5%52 VILLENEUVEd'ASQ (France)
Jean-Marie BASSET Instltut de Recherches Sur La Catalyse
2 Avenue Albert Einstein
69926 VILLEURBANNE CEDE! (France)
Lajos BENCZE Veszprem University of Chemical Engineering
H-8201 VESZPREM (Hungary)
Cetin BOZKURT Department of Chemistry
Hacettepe University
Beytepc Campus, 06532 ANKARA (Turkey)
Regina. BUFFON Instltut de Recherches Sur La. Ca.ta.1yse
2 Avenue Albert Einstein
69926 VILLEURBANNE CEDEX (France)
xi