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Ring Opening Metathesis Polymerisation and Related Chemistry
Ring Opening Metathesis Polymerisation and Related Chemistry
NATO Science Series
A Series presenting the results of scientific meetings supported under the NATO Science Programme.
The Series is published by lOS Press, Amsterdam, and Kluwer Academic Publishers in conjunction with the NATO Scientific Affairs Division
Sub-Series
I. Life and Behavioural Sciences II. Mathematics, Physics and Chemistry III. Computer and Systems Science IV. Earth and Environmental Sciences V. Science and Technology Policy
lOS Press Kluwer Academic Publishers lOS Press Kluwer Academic Publishers lOS Press
The NATO Science Series continues the series of books published formerly as the NATO ASI Series.
The NATO Science Programme offers support for collaboration in civil science between scientists of countries of the Euro-Atlantic Partnership Council. The types of scientific meeting generally supported are "Advanced Study Institutes" and "Advanced Research Workshops", although other types of meeting are supported from time to time. The NATO Science Series collects together the results of these meetings. The meetings are co-organized bij scientists from NATO countries and scientists from NATO's Partner countries - countries of the CIS and Central and Eastern Europe.
Advanced Study Institutes are high-level tutorial courses offering in-depth study of latest advances in afield. Advanced Research Workshops are expert meetings aimed at critical assessment of a field, and identification of directions for future action.
As a consequence of the restructuring of the NATO Science Programme in 1999, the NATO Science Series has been re-organised and there are currently Five Sub-series as noted above. Please consult the following web sites for information on previous volumes published in the Series, as well as details of earlier Sub-series.
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Series II: Mathematics, Physics and Chemistry - Vol. 56
Ring Opening Metathesis Polymerisation and Related Chemistry
State of the Art and Visions for the New Century
edited by
E. Khosravi IRC in Polymer Science and Technology, University of Durham, United Kingdom
and
T. Szymanska-Buzar Faculty of Chemistry, University of Wroclaw, Poland
.... " Springer-Science+Business Media, B.V.
Proceedings of the NATO Advanced Study Institute on Ring Opening Metathesis Polymerisation and Related Chemistry: State of the Art and Visions for the New Century Polaica-Zdroy, Poland 3-15 September, 2000
A C.I.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-1-4020-0559-6 ISBN 978-94-010-0373-5 (eBook)
DOI 10.1007/978-94-010-0373-5
Printed on acid-free paper
AII Rights Reserved © 2002 Springer Science+Business Media Dordrecht Originally published by Kluwer Academic Publishers in 2002 Softcover reprint of the hardcover 1st edition 2002 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 photocopying, recording or by any information storage and retrieval system, without written permission from the copyright owner.
NATO ADVANCED STUDY INSTITUTE
RING OPENING METATHESIS POLYMERISATION AND RELATED CHEMISTRY: STATE OF THE ART AND VISIONS FOR THE NEW CENTURY
3rd _ 15 th SEPT. 2000, POLAICA-ZDROJ, POLAND
CO-DIRECTORS:
DR. E. KHOSRAVI CCHEM FRSC
PROF. T. SZYMANSKA-BUZAR
ORGANISING COMMITTEE:
DR. E. KHOSRAVI
PROF. T. SZYMANSKA-BUZAR
PROF. R.H. GRUBBS
DR. A. BELL
PROF. B. MARCINIEC
PROF. A. DEMONCEAU
Interdisciplinary Research Centre in Polymer Science and Technology, Department of Chemistry, University of Durham, UK [email protected]
Faculty of Chemistry, University of Wroclaw, Poland [email protected]
Interdisciplinary Research Centre in Polymer Science and Technology, Department of Chemistry, University of Durham, UK
Faculty of Chemistry, University of Wroclaw, Poland
Chemistry & Chemical Engineering, California Institute of Technology, USA
Advanced Polymer Technologies, LLC, USA
Faculty of Chemistry, Adam Mickiewicz University, Poland
Laboratory of Macromolecular Chemistry and Catalysis, University of Liege, Belgium
TABLE OF CONTENTS
PREFACE
ACKNOWLEDGEMENTS
CONTRIBUTORS
PART I. RING OPENING METATHESIS POL YMERISA TION
ROMP AND RELATED CHEMISTRY: PAST, PRESENT AND FUTUTRE K. J. IVIN
MECHANISM OF RUTHENIUM BASED OLEFIN METATHESIS
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CATALYSTS 17 R.H. GRUBBS AND M. SANFORD
RUTHENIUM CATALYSTS FOR ROMP AND RELATED CHEMISTRY 23 A. MUHLEBACH, P. A. V AN DER SCHAAF,A. HAFNER, R. KOLLY, F. RIME AND H.J. KIMER
BLOCKINESS AND TACTICITY IN RING-OPENED METATHESIS POLYMERS 45
V. AMIR-EBRAHIMI, J. G. HAMILTON AND J. J. ROONEY*
HIGH-RESOLUTION NMR AND ROMP A. M. KENWRIGHT
PART II. APPLICATION OF RING OPENING METATHESIS POLYMERISATION
APPLICATION OF ROMP IN THE SYNTHESIS OF FUNCTIONAL POLYMERS: AN APPROACH TO NOVEL ORGANICIINORGANIC
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COMPOSITES 69 W. 1. FEAST, E. HERZOG, B. R. HEYWOOD, 1. L. MEG SON AND S. J. WILLIAMS
MACROMOLECULAR ENGINEERING USING RING OPENING METATHESIS POLYMERISATION 81
V. HEROGUEZ AND Y. GNANOU
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SYNTHESIS OF NEW MACROMOLECULAR ARCHITECTURES BASED ON RING OPENING METATHESIS POLYMERISATION AND ATOM TRANSFER RADICAL POL YMERISATION 91
A. DEMONCEAU, F. SIMAL, S. DELFOSSE AND A. F. NOELS
WELL-DEFINED CROSSLINKED MATERIALS VIA RESIN TRANSFER MOULDING (RTM)-ROMP 105
E. KHOSRAVI
NEW MATERIALS FROM THERMAL AND PHOTOINDUCED RING OPENING METATHESIS POL YMERISA TION (ROMP/PROMP) 117
A. MUHLEBACH, P. A. V AN DER SCHAAF AND A. HAFNER
NOVEL POLYMERIC MATERIALS VIA ROMP USING WELL-DEFINED INITIATORS 13~
E. KHOSRAVI
SYNTHESIS AND CHARACTERIZATION OF SCLC-HOMOPOLYMERS AND BLOCKCOPOLYMERS 143
K. VIERTLER, A. WEWERKA, L. NOIREZ AND F. STELZER
ROMP OF NORBORNENE DERIVATIVES OF AMINO-ESTERS AND AMINO-ACIDS 157
M.NORTH
ROMP OF NORBORNENE DERIVATIVES OF PEPTIDES AND NUCLEIC-ACIDS 167
M.NORTH
APPLICATION OF ROMP IN THE SYNTHESIS OF FUNCTIONAL POLYMERS: ELECTRO-ACTIVE POLYMERIC MATERIALS 177
W. J. FEAST
ROMP POLYMERS IN ELECTRONIC APPLICATIONS: CONJUGATED POLYMERS, POL YELECTROL YTES AND PHOTORESIST POLYMERS 185
F. STELZER, R. MUELNER, H. SCHLICK AND G. LEISING
ROMP IN THE SYNTHESIS OF WELL-DEFINED CATALYTIC SUPPORTS 195
M. R. BUCHMEISER
HIGH-PERFORMANCE MATERIALS FOR SEPARATION TECHNIQUES VIA ROMP 205
M. R. BUCHMEISER
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FREE RADICAL FORMING ACTIVITY OF THE GRUBBS CATALYST AND RELATED ORGANOMETALLICS 217
V. AMIR-EBRAHIMI, 1. G. HAMILTON, 1. NELSON, 1.1. ROONEY, A. D. ROONEY AND C. 1. HARDING
DUAL ACTIVITY OF RUTHENIUM COMPLEXES IN OLEFIN METATHESIS AND RADICAL REACTIONS 227
A. DEMONCEAU, F. SIMAL AND A. F. NOELS
APPLICATIONS OF THE OLEFIN METATHESIS REACTION TO INDUSTRIAL PROCESSES 247
F.LEFEBVRE
STEREO-SELECTIVITY OF MONOCYCLOOLEFIN RING-OPENING METATHESIS 263
V. I. BYKOV, D. V. REDKIN AND E. SH. FINKELSHTEIN
EFFECTIVE SYNTHESES OF NATURAL COMPOUNDS USING RING OPENING METATHESIS AS A KEY REACTION 275
V. I. BYKOV, A. R. GOLETIANI, T. A. BUTENKO, E. V. EGUPOV A AND E. SH. FINKELSHTEIN
PART III. ACYCLIC DIENE METATHESIS AND OTHER RELATED CHEMISTRY
METAL-CONTAINING POLYMERS VIA ADMET CHEMISTRY 285 F. 1. GOMEZ AND K.B. WAGENER
METATHESIS POLYCONDENSATION OF SUBSTITUTED p-DIVINYLBENZENES; A WAY TO EASILY PROCESSABLE p-PHENYLENE-VINYLENE (PV) OLIGOMERS WITH VALUABLE PROPERTIES 295
E. THORN-CSANYI
FUNCTIONALIZED POLYETHYLENE SYNTHESIS VIA ADMET CHEMISTRY 307
1. E. SCHWENDEMAN, M. D. WATSON, 1. A. SMITH, R. BRZEZINSKA AND K. B. WAGENER
ROMP AND ADMET POL YMERISA TION WITH CARBYNE COMPLEXES AS CATALYSTS 321
K. WEISS AND M. THUERING
SIL YLA TIVE COUPLING POL YCONDENSA TION (SCP) VS. ADMET POL YMERIZA TION OF DIVINYL SUBSTITUTED SILICON COMPOUNDS 331
B. MARCINIEC
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METATHESIS POLYMERISATION OF ALKYNES 341 K. WEISS AND C. WIRTH
POL YMERISA TION OF CYCLIC OLEFINS AND ALKYNES BY SEVEN-COORDINATE TUNGSTEN (II) AND MOLYBDENUM (II) COMPOUNDS 349
T. SZYMANSKA-BUZAR
STUDY OF THE ACTIVITY AND STEREO SELECTIVITY OF SOME MET ATHESIS CATALYSTS WITH ACYCLIC INTERNAL OLEFINS 365
F. LEFEBVRE, X. BORIES-AZEAU AND 1.-M. BASSET
APPLICATIONS OF OLEFIN METATHESIS IN THE OLEOCHEMISTRY 377 1. C. MOL
CROSS METATHESIS VS. SIL YLA TIVE COUPLING OF OLEFINS WITH VINYLSUBSTITUTED SILICON COMPOUNDS IN THE PRESENCE OF TRANSITION METAL COMPLEXES 391
B. MARCINIEC
PART IV. SHORT PRESENTATIONS
SYNTHESIS OF WELL-DEFINED GRAFT COPOLYMERS AND THEIR ORGANISATION AT THE AIR-WATER INTERFACE 407
A. F. MILLER AND R. W. RICHARDS
POL YMERISA TION OF UNCONVENTIONAL MONOSUBSTITUTED ACETYLENES WITH METATHESIS AND INSERTION CATALYSTS 417
H. BALCAR, 1. SEDLACEK, 1. ZEDNIK, 1. VOHLIDAL AND V. BLECHTA
SPECULATIONS ON THE POSSIBLE MECHANISM OF THE NEW ROUTES TO POLYMER SYNTHESIS BY FRIEDEL-CRAFTS METATHESIS CATALYTIC SYSTEMS 425
C. JOSSIFOV
MASS SPECTROMETRIC INVESTIGATION OF TERMINAL OLEFIN METATHESIS AND POLYMERIZATION ONTO W(CO)6 AND Mo(CO)JCC14, CBr4lhv CATALYST SYSTEMS IN GAS-PHASE 437
C. KA V AKLI AND B. SALIH
HETEROGENATION OF A SHIFF BASE SUBSTITUTED GRUBBS CATALYST AND A Ru-DIMER TO PERFORM ROMP REACTIONS 451
B. DE CLERCQ, T. OPSTAL, K. MELIS AND F. VERPOORT
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CAT AL YST ACTIVITY AND SELECTIVITY IN ROMP OF DICYCLO-PENTADIENE INDUCED BY SOME TUNGSTEN SYSTEMS 465
V. DRAGUTAN, I. DRAGUTAN, M. DIMONIE, C. COUVE ANDM. ABADIE
ULTRASOUND ASSISTED METATHESIS OF MONOCYCLIC OLEFINS WITH TUNGSTEN-BASED CATALYSTS 477
I. DRAGUTAN, V. DRAGUTAN, A. PETRIDE, M. VINATORU ANDP. FILIP
DFT STUDY ON ETHENE METATHESIS PROCEEDING ON Mo03/Alz03
CAT AL YST 483 J. HANDZLIK AND J. OGONOWSKI
SUBJECT INDEX 489
PREFACE
Since the last ASI in Turkey in Sept. 1995, the olefin metathesis has made remarkable strong developments with an incredible speed in various directions. New catalyst systems have been developed which have resulted in the synthesis of novel materials. Other fascinating developments have been the new catalysts for stereoselective metathesis and catalysts with considerable functional group tolerance. These new catalysts in addition to Ring Opening Metathesis Polymerisation (ROMP) and Acyclic Diene Metathesis (ADMET) are now powerful tools for Ring Closing Metathesis (RCM) and have found many applications in the synthesis of natural products. A lot of information has been established about all aspects of the olefin metathesis and there is a vast literature concerning the process, covering the initiators, mechanistic features and applications of this reaction in organic and polymer synthesis. The NATO ASI on ROMP and Related Chemistry took place in Polanica-Zdroj, Poland during 3rd to 15th
Sept. 2000, to highlight the developments in this area and to discuss the prospects and visions for the year 2000 and beyond. The aims of the ASI were: to provide a platform for dissemination of knowledge; to promote communication between people who have a serious interest in this field of chemistry; to help establishing international scientific contacts and to provide an opportunity for the scientists with an appropriate scientific background to learn of recent developments in this field of science. There were 15 lecturers and 67 participants in this NATO ASI. The selection of participants was based on their qualifications, whether presenting posters or oral presentations and the impact of attending the ASI on their future career. In selecting the participants a good balance was kept between the participants from the NATO Countries (58%) and from the Partner Countries (42%). High number of young scientists and particularly female scientists participated, which was very pleasing for the organising committee and for the lecturers. The lecturers were internationally recognised experts from academia and from industry and presented and discussed in details the recent exciting achievement. In addition to details of the lecturers' latest research findings, the presentations included an element of advanced teaching. There was a general agreement amongst the lecturers and the participants that the ASI was a complete success, in terms of the organisation, scientific programme, quality of the lectures, level of participation in questions and discussions and the relaxed environment for scientific and social discussions. This was clearly indicated during the meeting and also later on through email messages that received. This was very pleasing and very rewarding for the co-directors who have put lots of time and effort in organising this ASI. The meeting established that the success of olefin metathesis as a synthetic tool during the 20th century is attributed to outstanding advances in the field of catalysis and organometallic chemistry. The versatility of the metathesis reaction has been the key in attracting the attention of chemists with interests ranging from polymer chemistry to organic synthesis. The prospect for the new century in the area of olefin metathesis is very bright and very encouraging. There is no doubt that the olefin metathesis reaction
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is going to continue to intrigue chemists with respect to the many new polymers and new molecules that can be synthesised using this technique. In order to extend the benefit of this NATO ASI to those who did not have the opportunity to attend, the main lectures and some of the short presentations are published in this NATO ASI Series book.
Ezat Khosravi
ACKNOWLEDGEMENTS
The editors would like to sincerely thank NATO Scientific Affairs Division for awarding funds for organising the ASI on ROMP and Related Chemistry in Poland. The kind financial support of the following companies and organisations is also gratefully acknowledged. This non-NATO fund was used to finance some of the social evenings and also to support those participants who were not eligible for receiving NATO funds.
Strem Chemicals, USA Advanced Polymer Technology (APT), USA
CIBA Speciality Chemicals, Switzerland National Science Foundation, USA
Scientific and Technical Research Council of Turkey
The editors would also like to pass on, to NATO Scientific Affairs Division and other sponsors, the participants' thanks and gratitude for being given the opportunity to participate in the ASI and to learn of the latest development in this field of chemistry.
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H. BALCAR
1.-M. BASSET
M. R. BUCHMEISER
A. DEMONCEAU
I. DRAGUTAN
V.DRAGUTAN
W.1. FEAST
E. SH. FINKELSHTEIN
Y.GNANOU
CONTRIBUTORS
HeyrovskJ Institute of Physical Chemistry, Academy of Sciences of the Czech, Republic, 182 23 Prague 8, Czech Republic
Laboratoire de Chimie Organometallique de Surface, UMR CNRS-CPE 9986, 43 Bd du 11 Novembre 1918, 69626 Villeurbanne Cedex, France
Institut fUr Analytische Chemie und Radiochemie, Arbeitskreis Makromolekulare Chemie, Universitiit Innsbruck, Innrain 52a, A-6020 Innsbruck, Austria
Laboratory of Macromolecular Chemistry and Organic Catalysis, University of Liege, Sart-Tilman (B.6a), B-4000 Liege, Belgium
Institute of Organic Chemsitry of the Romanian Academy, 202B Spl. Independentei, Bucharest, Romania
Institute of Organic Chemsitry of the Romanian Academy, 202B Spl. Independentei, Bucharest, Romania
Interdisciplinary Research Centre in Polymer Science and Technology, Durham University, Durham DHI 3LE, UK
Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Leninsky prospect 29,117912 Moscow, Russia
Laboratoire de Chimie des Polymeres Organiques, CNRS - ENSCPB - Universite Bordeaux, 16, avenue Pey-Berland, 33607 PESSAC Cedex, France
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R. H. GRUBBS
J. HANDZLIK
K. J. IVIN
C. JOSSIFOV
A. M. KENWRIGHT
E. KHOSRAVI
F. LEFEBVRE
B. MARCINIEC
A. F. MILLER
J. C. MOL
A. MUHLEBACH
M.NORTH
J. 1. ROONEY
Division of Chemistry and Chemical Engineering, 164-30, California Institute of Technology, Pasadena, CA 91125, USA
Institute of Organic Chemistry and Technology, Cracow University of Technology, ul. Warszawska 24, PL 31-155 Krakow, Poland
12, St. Michael's Gardens, South Petherton, Somerset, TAI35BD, UK
Institute of Polymers, Bulgarian Academy of Sciences, 1113 Sofia, Bulgaria
Department of Chemistry, University of Durham, Durham DHI 3LE, UK
Interdisciplinary Research Centre in Polymer Science and Technology, Durham University, Durham DHI 3LE, UK
Laboratoire LCOMS, UMR CNRS-CPE 9986, 43 Bd du 11 Novembre 1918, 69626 Villeurbanne Cedex, France
Department of Organometallic Chemistry, Faculry of Chemistry, Adam Mickiewicz University, 60-780, Poznan, Poland
Interdisciplinary Research Centre in Polymer Science and Technology, Durham University Durham DHI 3LE, UK
Institute of Molecular Chemistr, Faculty of Science, Universiteit van Amsterdam, Nieuwe Achtergracht 166, 1018 WV Amsterdam, The Netherlands
Ciba Specialty Chemicals Inc., Additives Division, CH-4002 Basel, Switzerland
Department of Chemistry, King's College, Strand, London, WC2R 2LS, UK
School of chemistry, The Queen's University of Belfast, Belfast BT9 SAG, N. Ireland, UK
B. SALIH
F. STELZER
T. SZYMANSKA-BUZAR
E. THORN-CSANYI
F. VERPOORT
K. B. WAGENER
K. WEISS
Chemistry Department, Science Faculty, Hace~tepe Universit, Beytepe Campus, 06532 Ankara, Turkey
Institute for Chemistry and Technology of Organic Materials, Graz University of Technology, Stremayrgasse 1611, 8010 Graz" Austria
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Institute of Chemistry, University of Wroclaw, ul. F. Joliot-Curie 14, 50-383 Wroclaw, Poland
Institute of Technical and Macromolecular Chemistry, University of Hamburg, Bundesstr. 45, D-20I46 Hamburg, Germany
Department of Inorganic and Physical Chemistry,Ghent University, Krijgslaan 281, 9000 Ghent, BELGIUM
George & Josephine Butler Polymer Research Laboratory, Department of Chemistry, University of Florida, Gainesville, FL 32611-7200, USA
University of Bayreuth, Department of Inorganic Chemistry I, D-95440 Bayreuth, Germany
