Catalytic Synthesis of Alkene-Carbon Monoxide Copolymers and Cooligomers

329 Pages·2003·7.15 MB·English

by  Ayusman Sen (auth.)

CATALYTICSYNTHESISOFALKENE-CARBONMONOXIDE
COPOLYMERSANDCOOLIGOMERS
Catalysis by MetalComplexes
Volume27
Editors:
BrianJames,UniversityofBritishColumbia,Vancouver, Canada
PietW.N.M.vanLeeuwen,UniversityofAmsterdam,TheNetherlands
AdvisoryBoard:
AlbertS.c.Chan,TheHongKongPolytechnicUniversity, HongKong
RobertCrabtee, YaleUniversity, U.S.A.
DavidCole-Hamilton,UniversityofStAndrews,Scotland
IstvanHorvath,EorvosLorandUniversity, Hungary
KyokoNozaki,UniversityofTokyo,Japan
RobertWaymouth,StanfordUniversity, U.S.A.
CATALYTIC SYNTHESIS
OF ALKENE-CARBON
MONOXIDE COPOLYMERS
AND COOLIGOMERS
cdited by
Ayusman Sen
Departmelll of Chem;slry.
n,e Pellmyll'mria Srate Uni\'ersily. u.S.A.
SPRINGER-SCIENCE+BUSINESS MEDIA, B.V.
A C.T.P. Catalogue record for this book is available from the Library of Congress.
ISBN 978-1-4613-4866-5 ISBN 978-1-4419-9266-6 (eBook)
DOI 10.1007/978-1-4419-9266-6
Printed on acid-free paper
AII Rights Reserved
© 2003 Springer Science+Business Media Dordrecht
Originally published by Kluwer Academic Publishers in 2003
Softcover reprint of the hardcover 1 st edition 2003
No part of this work may be reproduced, slored in a retrieval system, Of transmitted
in any form or by any means, electronic, mechanical, photocopying, microfilming, rccording
or otherwise, without written permission from the Publisher, with the exception
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and execuled on a computer system, for exclusive use by the purchaser of the work.
Contents
Chapter1. IntroductionandFutureDirections
AyusmanSen
1. INTRODUCTION 1
2. FUTUREDIRECTIONS 4
Chapter2. Palladium-CatalysedSynthesisofMono-esters,-ketones,and- 9
aldehydes/alcohols
Robert1.PughandEiteDrent
1. iNTRODUCTION 9
2. METHOXYCARBONYLATION II
2.1. Di-tert-butyldiphosphinesasligands 12
2.2. Bi-andtricyclicalkyldiphosphinesasligands 15
2.2.1. Phospha-bicyclo-nonanes 15
2.2.2. I,3,5,7-tetramethyl-4,6,8-trioxa-2-phospha-adamantanes 16
3. PRECISECONTROLOFTHEOXO-SYNTHESIS 17
3.1. Chemoselectivity 18
3.1.1. Elementarystepsinhydrocarbonylation 21
3.1.2. Theinterplayofligandsandanions:palladium 22
electrophilicity
3.1.3. Hydroformylationvs.hydroacylation 23
3.2. Regioselectivityinpalladium-catalyzedoxo-synthesis 26
3.2.1. Observations 26
3.2.2. Discussion 28
3.3. Highlyefficientpalladiumcatalystsforthehydroformylationof 29
internalolefinstolinearalcohols
3.4. Conclusions 31
vi
Chapter3. ProductionofCooligomersfromCarbonMonoxideandEthene 37
DavidJ.Cole-HamiltonandRuthA.M.Robertson
I. INTRODUCTION 37
1.1. Production of methyl propionate or polyketones from ethene 37
andcarbonmonoxide
1.2. ControllingchaingrowthtogivecooligomersofetheneandCO 39
1.2.1. Increasingchaingrowthusingmonodentateligands 39
1.2.2. Inhibitingchaingrowthusingbidentateligands 40
1.2.3. Selectiveformationof3-pentanone 41
2. OLIGOKETONESYNTHESIS 43
2.1. Unidentatephosphines 43
2.1.1. Extendingchaingrowththroughcontrollingthereaction 43
conditions
3. BlDENTATELIGANDS 49
3.1. Restrictingchaingrowththroughtheligandbackbone 49
3.1.1. Generalconsiderations 49
3.1.2. Alternativemechanismleadingtoearlyterminationof 53
chaingrowth
3.1.3. Proposedmechanismfortheformationofmethyl 54
propionatecatalyzedbypalladiumcomplexesof
BU(2PCH2C6H4CH2PBu(2orBU(2P(CH2)3PBu(2
3.1.4. Proposedmechanismsofcooligomerizationusing 57
diphosphineswithdifferentback-bonelengths
4. TERMINATIONMECHANISMS 58
5. CONTROLLINGCHAINGROWTHTHROUGHTHEUSEOFALTERNATIVE 61
METALS
5.1. Rhodiumbasedcatalysts 61
5.1.1. Effectsofelectrondensityonrhodiumuponproduct 61
distributions
5.1.2. Theoriginofhydrogenatomsfortheproductionof 62
diketoneproducts
5.1.3. Theeffectofaddedbasesontheproductdistributionusing 64
electronpoorrhodiumcatalysts
5.1.4. Terminationmechanismsforrhodiumbasedcatalysts 66
5.1.5. Theanomalousreducedyieldof3-pentanonewhenusing 67
electronpoorrhodiumcatalysts
5.1.6. Increasedselectivitytocooligomerizationinelectronrich 73
rhodiumsystemsthroughliganddesign
5.2. Metalsotherthanpalladiumorrhodium 77
6. SELECTIVEFORMATIONOF3-PENTANONE 78
6.1. Rhodiumbasedcatalysts 78
6.2. Palladiumbasedsystems 78
vii
6.3. Cobaltbasedsystems 79
6.4. Formationof3-pentanoneunderhydroformylationconditions 82
7. CONCLUSIONS 82
Chapter4. CatalyticSynthesisofCopolymersandTerpolymers 87
W.P.Mul,A.W.vanderMade,A.A.Smaardijk,andE.Drent
1. INTRODUCTION 87
2. PHYSICALPROPERTIESOFALIPHATICPOLYKETONES 88
3. COPOLYMERIZATION 90
3.1. PerfectlyAlternatingCopolymers 90
3.2. CatalystsforCOla-olefincopolymerization 93
3.2.1. Palladium-basedcatalysts 93
3.2.2. Nickel-basedcatalysts 96
3.3. Non-perfectlyalternatingcopolymers 97
3.4. MechanisticAspects 98
3.4.1. Propagation 98
3.4.2. InitiationandTermination 100
4. PROCESSDEVELOPMENT 103
4.1. Developmentofacatalystforthecommercialprocess 103
4.2. Processandproductconsistency 105
4.3. Manufacturingprocess 106
5.DETAILEDINvESTIGATIONOFLIGANDEFFECTS 107
5.1. Theeffectofphosphinesubstituents 109
5.1.1. Electroniceffects 109
5.1.2. Stericeffects 111
5.1.3. Kineticaspects 112
5.2. Theeffectofthebridgestructure 113
5.2.1. Bridgelength 113
5.2.2. Theeffectofbridgesubstituents 113
5.2.2.1. BridgesubstituenteffectsinDPPP-typeligands 114
5.2.2.2. BridgesubstituenteffectsinDapp-typeligands 115
5.2.3. Effectofthebridgestructureonkinetics 116
6. THEPHYSICALSTATEOFTHECATALYST 118
7. INITIALCATALYSTPERFORMANCE 120
7.1. Quenchedflow 120
7.2. Quenchedflowobservations 122
7.3. Rate drop and polymer morphology build up in batch slurry126
polymerizations
7.4. On the possible molecularorigin ofligand bridge substituent127
effects
8. ONTHEPOSSIBLEROLEOFOXIDANTPROMOTORS 128
viii
9. SUMMARYANDOUTLOOK 131
Chapter5. ChainTransferMechanisms 141
PietW.N.M.vanLeeuwen
1. INTRODUCTION 141
1.1. History 141
1.2. Elementarystepsformakinginitiatingspecies 142
1.3. Elementarystepsforchaintransferreactions 148
1.4. Switchingoftheinitiators 153
1.5. Dormantstates 155
2.POLYMERIZATIONS 156
2.1. Etheneandcarbonmonoxide 156
2.2. Phosphineligandeffectsforetheneandcarbonmonoxide 164
2.3. Etheneandcarbonmonoxideinaproticsolvents 167
2.4. Propeneandcarbonmonoxide 168
2.5. Styreneandcarbonmonoxide 168
3. OLIGOMERIZATIONS 171
3.1. Ethene,carbonmonoxideandwater 171
3.2. Styrene,carbonmonoxide,anddihydrogen 172
3.3. Ethene,propeneandcarbonmonoxide 173
4. FORMATIONOFESTERSANDACIDS 174
4.1. Hydrocarbonylation 174
4.2. Methoxycarbonylationofethene 178
4.3. Methoxycarbonylationofothersubstrates 184
Chapter6. StereochemicalAspectsofCooligomerizationand 189
Copolymerization
GiambattistaConsiglioandBarbaraMilani
1. INTRODUCTION 189
2. AROMATICOLEFINS(STYRENE) 191
2.1. C -Symmetryligands 191
2u
2.2. C,-Symmetryligands 193
2.3. CrSymmetryligands 194
2.4. CrSymmetryligands 196
3. ALIPHATICOLEFINS(PROPENE) 202
3.1. Regio-andstereoirregularcopolymers 202
3.2. Regio-andstereoregularcopolymers 202
4. CYCLOPOLYMERIZATION 210
5. FINALREMARKS 213
Chapter7. SynthesisofChiral,OpticallyActiveCopolymers 217
KyokoNozaki
ix
I. INTRODUCTION 217
2. COPOLYMERIZATIONOFPROPENEORHIGHERI-ALKENESWITH 218
CARBONMONOXIDE
2.1. Ligandsandpolymerizationconditions 218
2.2. Spiroketalformation 221
2.3. Enantioselectivity 222
2.4. HigherI-Alkenes 226
3. COPOLYMERIZATION OF STYRENE OR ITS DERIVATIVES WITH226
CARBONMONOXIDE
4. COPOLYMERIZATIONOFOTHEROLEANSWITHCARBONMONOXIDE 230
5. ASYMMETRICTERPOLYMERIZATIONOFMORETHANTwoKINDSOF232
OLEFINSWITHCARBONMONOXIDE
6. POLYKETONECONFORMATION 233
7. CONCLUSION 234
Chapter8. ChainPropagationMechanisms 237
AyusmanSen
1. INTRODUCTION 237
2. PALLADIUM(II)BASEDSYSTEMS 238
3. NICKEL(II)BASEDSYSTEMS 256
4. RHODIUM(I)BASEDSYSTEMS 257
5. CONCLUSION 261
Chapter9. TheoreticalStudiesonCopolymerizationofPolarMonomers 265
PeterMargl,ArturMichalak,andTomZiegler
1. INTRODUCTION 265
2. COPOLYMERIZATIONOFCARBONMONOXIDEWITHETHYLENE 267
2.1. Experimentalandcalculatedratesfortheinsertionprocessesfor267
copolymerizationcatalysedbyPd(II)systems.
2.2. A moredetailedlookattheproductiveandunproductivecycles270
incopolymerizationcatalysedbyPd(II)complexes.
2.2.1. Theproductivecycle 270
2.2.2. C2H4misinsertionintoanethyleneterminatedpolyketone 275
chain
2.3. Experimentalandcalculatedratesfortheinsertionprocessesfor277
alternatingcopolymerizationcatalyzedbyNi(II)systems
3. COPOLYMERIZATIONOFOLEFINSWITHPOLARMONOMERSOTHER 280
THANCO
3.1. Preferredbindingmodeofoxygencontainingmonomers 282
3.2. Preferredbindingmodeofnitrogencontainingmonomers 285
3.3. Ethylene-methylacrylatecopolymerizationcatalyzedbyPd- 287
baseddiiminecatalysts.
x
3.4. Ethylene-MethylAcrylateCopolymerizationCatalyzedbyNi- 303
basedDiimineCatalysts
4. CONCLUDINGREMARKS 305
Index 309