Oletin Metathesis and Polymerization Catalysts

NATO ASI Series Advanced Science Institutes Series

A Ser ies 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 B Physics

C Mathematical and Physical Sciences

D Behavioural and Social Sciences E Applied Sciences

F Computer and Systems Sciences G Ecological Sciences H Cell Biology

Plenum Publishing Corporation London and New York

Kluwer Academic Publishers Dordrecht, Boston and London

Springer-Verlag Berlin, Heidelberg, New York, London, 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 Ad vance d Stu dy Institu te on Dlefin Metathesis and Polymer izatlon

Ca talysts: Synt hesi s . Mec hanis m. and Ut ilizat ion (1989 Ak ,ay. Tu rkeyl

Dlefin metathesis and polymerization catalysts : synthesis. mechanism. and uti I ization : proceedlngs of the NATD Advanced Study Institute on Dlef l n Metathesis and Polymerization Catalysts­- Synthesis . Mec hanis m. and Uti lization. Ak,a y. Turkey . Septe mber 10-22. 1989 / ed ited by Yavu2 imamo glu , Birg u1 Zumreog lu-Ka ran, and AI1an J. Am ass.

p. cm. -- (NATO ASI ser i es . Seri es C, Mathematical and phys ical sciences ; val. 3261

Includes index.

1. Cata ly sis--Co ngres se s. (Chemlstry l--Co ngresses. 4. 1. imamog I u. Yav uz. 1945-III. Amass. Alia n J .• 1943-

2. Alkenes --Con gre sses . 3. Metathesis Polyrnerizat ion--Co ng resses .

II. Zumr eoglu-Karan, Bi rgu l, 1955-IV. Title. V. Ser ies: NATD ASI

series. Series C, Mathematical and physical sciences ; no. 326. OD505.N365 1989 660' .2995--dc20

ISBN 978-94-010-5470-6

Printed on acid-free paper

AII Rights Reserved © 1990 Springer Science+Business Media Dordrecht Orig inally published by Kluwer Academic Publishers in 1990 Softcover reprint of the hardcover 1 st edition 1990

90-20345

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.

ISBN 978-94-010-5470-6 ISBN 978-94-011-3328-9 (eBook)DOI 10.1007/978-94-011-3328-9

TABLE OF CONTENTS

PREFACE

List of Participants

OVERTURE: Olefin Metathesis and Metathesis Polymerization , A Historical

Perspective

K.J. Ivin, UK

PART 1. HOMOGENEOUS SYSTEMS

The Stereochemistry of Metathesis of Acyclic and Cyclic Olefins

J-M. Basset .... D. Boutarfa, E. Custodero, M. Leconte and C. Palliet

Electrochemical Generation of Catalysts for Alkene Metathesis

S. Bages, M. Petit, A. Mortreux and F. Petit'"

Catalysts for the Hom.ogeneous Metathesis of Functionalized Ole fins

J,C. Mol

Block Copolym.ers by Anionic to Metathesis Transformation Reactions

A.J. Amass" . D. Gregory, B.J. Tighe and M.A. Tyler

The Kinetics of Polymerization of Cyclopentene

A.J. Amass". M. Lotfipur, B.]. Tighe. C.N. Tuck and lA. Zurimendi

Tacticity in Polymers Initiated by Metathesis Polymerization: Effect of

Catalyst

K.J.Ivin

Degradation of Polymers by Metathesis Catalysts

K. Hummel

1X

xi

1

45

89

115

lil

167

187

209

vi

Metathesis Polymerization by Homogeneous Catalysts: Simulations

L. Bencle

PART II. HETEROGENEOUS SYSTEMS

General Properties of Supported Metathesis Catalysts

JC Mol

Surface Funclionalization of Supported Catalysts

K,Tanaka

Novel Supported Catalysts for Terminal Alkene Metathesis

K,Tanaka

Characterisation of Rhenium Oxide! Alumina MetathesiS Catalysts

A. Ellison

Stoichiometric Reactions with Reduced Phillips Catalysts

H.L. Krauss"'. E. Amberger, N. Arfsten, P. BlOme!. W. Hammon,

R. Hopfl and W. Riederer

Catalytic Reactions with Reduced Phillips Catalysts

HL Krauss". B. Frank. B. Hanke, E. Hums, D. Langstein,

D. Naumann, B, Siebenhaar and K. Weiss

Non-Chromium Surface Compounds

HLKrauss*, G Guldner, M. Hornscheldt, N, Larsen, R. Merkel.

P. Morys, S. Schmerbeck and P. Zahn

Coordination Chemistry of Silica Supported Cr Ions:

Types of CrUn Ions on Reduced Samples

E, Garrone*, G. Ghiotti and A. Zecchina

24i

"''''1 /.Ii

303

359

373

383

393

Structural Analysis of Supported Chromium Systems

A. Ellison

PART III, INDUSTRIAL ASPECTS

Induslrial Aspects of Olefin Metathesis I Polymerization Catalysts

R Streck

1. Historical Development

2, Present Industrial Status and Outlook

3. Technological Properties and Applications of Metathesis Polymers

PART IV. SHORT CONTRIBUTIONS

1. Papers

Syntheses of Heterogeneous. Bimetallic Metathesis Catalysts by Reactions

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

Heterogeneous Carbene Tungsten(VI:l Complexes

K,Weiss"', G. Ll:lssel and M, Denzner

Aqueous Ring-Opening Metathesis Polymerizations of 7-0xa-norbornene

Derivat1ves Usmg Ruthenium Catalysts

D,V. McGrath"', B.M. Novak. and R.H, Grubbs

The Application of Ring Opening Metathesis Polymerization to ~he

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

vii

407

439

457 489

517

)21

323

337

viii

Raman Spectroscopy of Chromium Oxide Supported on Alumina, Titania

and Silica: A Comparative Study

F.D. Hardcastle" and I.E. Wachs

Stoichiometric and Catalytic Carbene Complex Reactions with the

Reduced Phillips Catalyst

f.. Weiss

Metathesis-Like Reactions of Heteroalkenes and Het.eroallenes

with the Ca.rbyne Complex C13(dme)W=CCMe3

K. Weiss* and R. Goller

Catalytic Metathesis of Alkynes

S.Bages. M.Petit*. A. Mortreaux and F. Petit

Electrochemical Synthesis of Catalytic Spedes for Alkene Metathesis

S. Bages*, M.Petit, A. Mortreaux and F. Petit

Chromium Supported Catalysts for Ethylene Gas Phase Polymerization

JR.G. Velasco", M.A.G. Ortiz. JI.G. Ortiz. J.A.G. Marcos and j.I.A. Uriarte

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

Norbornadiene and Cyc10pentene

B. DOz*. C. Bozkurt and Y. Imamoglu

PART V. RESEARCH PROSPECTS

INDEX

545

537

549

)51

553

5'55

»7

5)9

561

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

Allan J. AMASS

Elisabeth AMBERGER

Sylvie BAGES

Jean-Marie BASSET

Lajos BENCZE

Cetin BOZKURT

Regina. BUFFON

Department of Chemistry

KSZim Karabeldr Education Faculty

AtatOrk University. ERZURUM (Turkey)

Department of Chemical Engineering and Applied Chemistry

Aston University

GostaGreen. BIRMINGHAM B47IT <UK)

Laboratorium fOr Anorganische Chemie

Universitaet Bayreuth

Postfach 10 1251, 8580 BAYREUTH (Germany)

Ecole National Superior de Chimie

BP 108.5%52 VILLENEUVEd'ASQ (France)

Instltut de Recherches Sur La Catalyse

2 Avenue Albert Einstein

69926 VILLEURBANNE CEDE! (France)

Veszprem University of Chemical Engineering H-8201 VESZPREM (Hungary)

Department of Chemistry

Hacettepe University

Beytepc Campus, 06532 ANKARA (Turkey)

Instltut de Recherches Sur La. Ca.ta.1yse

2 Avenue Albert Einstein

69926 VILLEURBANNE CEDEX (France)

xi

xii

Jean Luc COUTURIER

Henri CRAMAIL

Naci CANKAYA

Herminio DIOGO

BOlentDUZ

Alan EllISON

Edoardo GARRONE

Eric j. GINSBURG

AhmetGULCE

Instttut de Recherches Sur La. Ca.ta.lyse

2 Avenue AlbertEinstein 69926 VILLEURBANNE CEDEX (}o'ra.nce)

L.C.P.O. Universite Bordeaux I

33405 TALENCE CEDEX (France)

Department of Chemistry

Hacettepe University

Beytepe Campus. 06532 ANKARA (Turkey)

Centro de OuimicaEstrutural. Complexo I

Instituto Superior Tecnico

Av. Rovisco Pais. 1096 LISBOA CODEX (Portugal)

Department of Chemistry

Hacettepe University

Beytepe Campus. 06532 ANKARA (Turkey)

Humberside College of Higher Education

Cottingham Road. HULL HU6 7RT (UK)

Department of Inorganic Chemistry

University ofTorino

Via P.Giuria 7. 10125 TORINO (Italy)

CALTECH 16430

Division of Chemistry and Chemical Engineering

Pasadena. CMl12j (USA)

Department of Chemistry

Hacettepe University

Beytepe Campus. 06532 ANKARA (Turkey)

Ali GUNER

Ahmet GURSES

Franklin D. HARDCASTLE

Valerie HEROGUEZ

Jukka HIETALA

Ida Marcia HOHN

Klaus HUMMEL

fero IlSKOLA

Ken J. IVIN

Department of Chemistry

Hacettepe University

Beytepe Campus. 06532 ANKARA (Turkey)

Department of Chemistry

Kazlm Karabekir Education Faculty

AtatOrk University. ERZURUM (Turkey)

Sinclair Lab. 7

Lehigh University

BETHLEHEM. PA 180185 (USA)

L.C.P.O. Universite Bordeaux I

33405 TALENCE CEDE! (France)

Neste Oy Chemicals P.O.Box 320, SF06101 PORVOO (Finland)

Department of Chemical Engineering and

Applied Chemistry, Aston University

GostaGreen, BIRMINGHAM B47ET (UK)

Institute of Chemical Technology

Technical Univensity of Graz

Stremayrgasse 16, A8010 GRAZ (Austria)

Neste Oy Chemicab

P.O.Box 320. SF06101 PORVOO (Finland)

The Queen's University of Belfast Department of Chemistry

12 St. Michael's Gardens, South Petherton

SOMERSET TA 13 JBD (UK)

xiii

xiv

YavuzIMAMOCLU

Jorge JUSTINO

CemalKAYA

AbdOlkerim KARABAKAN

Hasan KOCAOKUTGEN

Hans L. KRAUSS

Benoit LEPREVOST

Gianmario MARTRA

Dominic V. McGRATH

Department of Chemistry

Hacettepe University

Beytepe Campus. 06532 ANKARA (Turkey)

Centro de QuimicaEstrutural. Complexo 1

Instituto Superior Tecnico

Av. Rovisco Pais. 10% LISBOA CODEX (Portugal)

Department of Chemistry

Cumhuriyet University. '58140 StVAS (Turkey)

Department of Chemistry

Hacettepe University

Beytepe Campus. 06'532 ANKARA (Turkey)

Department of Chemistry

Ondokuz MaYls University

Kurupelit, SAMSUN (Turkey)

Laboratorium fOr Anorganische Chemie

Universitaet Bayreuth

Postfach 10 12 '51, 8580 BAYREUTH (Germany)

Ecole National Superior de Chimie

BP 108.59652 VILLENEUVE d'ASQ (France)

Department of Inorganic Chemlstry

University ofTorino

Via P.Giuria 7. 10125 TORINO (Italy)

CALITeH 16430

Division of Chemistry and Chemical Engineering

Pasadena, CMH2) (USA)

Johannes C. MOL

Gerald P. NICCOLAI

Francis PETIT

Michele PETIT

Maarten PLUGGE

EmsalPULAT

Melanie REICHELT

Davinder Singh RIAT

Department of Chemical Technology

University of Amsterdam

Nieuve Achtergracht 166.

AMSTERDAM (The Netherlands)

Department of Chemistry

University of Wisconsin

xv

1101 Unlv. Avenue. MADISON W153706 (USA)

Ecole National Superior de Chimie

BP lOS. 59652 VILLENEUVE d'ASQ (France)

Ecole National Superior de Chimie BP 108.5%52 VILLENEUVE d'ASQ (France)

Department of Chemical Technology

University of Amsterdam

Nieuve Achtergracht 166.

AMSTERDAM (The Netherlands)

Department of Chemistry

University of Ankara

Be~vler, ANKARA (Turkey)

Instltut de Recherches Sur La Cata.lyse

2 Avenue AlbertEinstein

69926 VILLEURBANNE CEDE! (France)

Department of Chemical Engineering and

Applied Chemistry Aston University

GostaGreen, BIRMINGHAM B47ET (UK)

xvi

BekirSALlH

Piet G.M. SCHILDER

Berndt SlEBENHAAR

Roland STRECK

Katsumi TANAKA

Nazan TUNOGLU

Canan UNALERoGLU

JR. Gonzales VELASCO

Department of Chemistry

HaceUepe University

Beytepe Campus, 06532 ANKARA (Turkey)

Department of Chemical Technology

University of Amsterdam

Nieuve Achtergracht 166,

AMSTERDAM (The Netherlands)

Laboratorium fOr Anorganische Chemie

Universitaet Bayreuth

Postfach 101251, 8580 BAYREUTH (Germany)

HolsAG

Leverkusener Strasse 12

D 4370 MARL (Germany)

Department of Electronics Engineering

The University of Electro-Communications 1-5-1, Chofugaoka. Chofu

TOKYO 182. (japan)

Department of Chemistry

HaceUepe University

Beytepe Campus. 06532 ANKARA (Turkey)

Department of Chemistry

Hacettepe University

Beytepe Campus. 06532 ANKARA (Turkey)

Univ. del Pais Vasco Unibertsitatea

Faculdad de Ciencias. Dipt. Ing. Quim.

BILBAO (Spain)

Karin WEISS

PeterWOUF

Helmuth WURM

Mine YALCINKAYA

BirgOI ZtrMREOGLU-KARAN

Laboratorium fOr Anorganische Chemie

Universitaet Bayreuth

xvii

Postfach 10 1251. 8580 BAYREUTH (Germany)

Laboratorium fOr Anorganischc Chemie

Universitaet Bayreuth

Postfach 10 1251. 8)80 BAYREUTH (Germany)

University of Hannover

Institute of Macromolecular Chemistry

Am Kleinen Felde 30, D3000 HANNOVER (Germany)

Department of Chemistry

Anadolu University

ESKISEHIR (Turkey)

Department of Chemistry

Hacettepe University

Beytepe Campus, 06532 ANKARA (Turkey)