Stereoselective Polymerization With Single-Site Catalysts Baugh Canich

698 Pages·2004·10.475 MB·English

Edited by
Lisa S. Baugh
JoAnn M. Canich
Stereoselective
Polymerization
with
Single-Site
Catalysts
CRC Press is an imprint of the
Taylor & Francis Group, an lnfonn• business
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Stereoselective
Polymerization
with
Single-Site
Catalysts
Edited by
Lisa S. Baugh
Jo Ann M. Canich
f:2...cRC
Press
~ Taylor & Francis Group
Boca Raton London New York
CRC Press is an imprint of the
Taylor &: Francis Group, an lnforma business
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On the cover is a space-filling model of an active rac-ethylenebis(indenyl)zirconium catalyst with an attached growing
polypropylene chain. This represents one of the first discoveries of an ansa-metallocene catalyst capable of producing
isotactic polypropylene. The transition structure of the modified Green-Rooney propylene insertion mechanism is also
depicted. The enantioselectivity of the propylene insertion step requires a catalyst with both appropriate symmetry and
stereorigidity.
The cover background photograph shows a reactor in the laboratory of Professor Stephen A. Miller, containing syndiotac
tic polypropylene prepared by graduate student Levi J.lrwin. The Miller-Bercaw metallocene catalyst employed (catalyst
s-90 in Chapter 2) is one of the most syndioselective propylene polymerization catalysts currently known. Unlike isotac
tic polypropylene, which can also be prepared with Ziegler-Natta initiators, syndiotactic polypropylene is only obtained
in appreciable quantities using single-site catalysts.
Cover design by Stephen A. Miller
CRCPress
Taylor & Francis Group
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Boca Raton, FL 33487-2742
@ 2008 by Taylor & Francis Group, LLC
CRC Press is an imprint of Taylor & Francis Group, an Informa business
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Library of Congress Cataloging-in-Publication Data
Stereoselective polymerization with single-site catalysts I edited by Lisa S. Baugh and JoAnn M.
Canich.
p.cm.
Includes bibliographical references and index.
ISBN-13: 978-1-57444-579-4 (hardcover: acid-free paper)
ISBN-10: 1-57444-579-0 (hardcover: acid-free paper)
1. Polymerization--Research. 2. Polymer engineering--Research. 3. Stereochemistry--Research. 4.
Catalysis--Research. I. Baugh, Lisa S. (Lisa Saunders) II. Canich, JoAnn M.
TP156.P6S74 2008
668.9'2--dc22 2007018734
Visit the Taylor &c. Francis Web site at
http://www.taylorandfrancis.com
and the CRC Press Web site at
http://www.crcpress.com
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Contents
Preface.............................................................................................. ix
Editors.............................................................................................. xiii
Contributors....................................................................................... xv
I Polypropylene:CatalystsandMechanism ............................................ 1
Chapter1 IsotacticPolypropylenefromC -andPseudo-C -SymmetricCatalysts......... 3
2 2
RekoLeinoandShirleyLin
Chapter2 Fluorenyl-ContainingCatalystsforStereoselectivePropylene
Polymerization...................................................................... 37
CraigJ.Price,LeviJ.Irwin,DavidA.Aubry,andStephenA.Miller
Chapter3 SubstitutedIndenylandCyclopentadienylCatalystsforStereoselective
PropylenePolymerization.......................................................... 83
JohnJ.Esteb
Chapter4 DoublyBridgedMetallocenesforStereoselectivePropylene
Polymerization...................................................................... 101
DeannaL.Zubris
Chapter5 MetalloceneswithDonor/AcceptorandOtherHeteroatomBridgesfor
StereoselectivePropylenePolymerization......................................... 135
PamelaJ.Shapiro
Chapter6 StereoselectivePropylenePolymerizationwithEarlyandLateTransition
MetalCatalysts...................................................................... 157
HaruyukiMakioandTerunoriFujita
Chapter7 CatalystStructureandPolymerTacticity:TheTheoryBehindSiteControlin
PropylenePolymerization.......................................................... 169
AnthonyK.Rappé,OlegG.Polyakov,andLynnM.Bormann-Rochotte
II Polypropylene:ApplicationsofTacticity............................................. 201
Chapter8 StereoblockPolypropylene......................................................... 203
VincenzoBusico
Chapter9 ElastomericHomo-Polypropylene:SolidStatePropertiesandSynthesisvia
ControlofReactionParameters.................................................... 231
SabineHild,CeciliaCobzaru,CarstenTroll,andBernhardRieger
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Chapter10 ControlofMolecularWeightandChain-EndGroupinTacticPolypropylenes
UsingChainTransferAgents....................................................... 273
T.C.Chung
Chapter11 FunctionalizationofTacticPolypropylenes ....................................... 297
ManfredBochmann
Chapter12 InfluenceofTacticityofPropylenePlacementonStructureandPropertiesof
Ethylene/PropyleneCopolymers................................................... 313
MaurizioGalimbertiandGaetanoGuerra
III OtherMonoolefinMonomers.......................................................... 343
Chapter13 StereocontrolinthePolymerizationofHigherα-OlefinMonomers ............. 345
MosheKol,SharonSegal,andStanislavGroysman
Chapter14 TacticPolystyreneandStyreneCopolymers....................................... 363
HaiyanMaandJilingHuang
Chapter15 CyclopenteneHomo-andCopolymersMadewithEarlyandLateTransition
MetalCatalysts...................................................................... 399
NaofumiNaga
Chapter16 TacticNorborneneHomo-andCopolymersMadewithEarlyandLate
TransitionMetalCatalysts.......................................................... 413
WalterKaminskyandMichaelArndt-Rosenau
IV DieneMonomersandOlefin-ContainingPolymers............................... 445
Chapter17 TheStereoselectivePolymerizationofLinearConjugatedDienes............... 447
AntonioProtoandCarmineCapacchione
Chapter18 TheStereoselectivePolymerizationofCyclicConjugatedDienes............... 475
MitsuruNakano
Chapter19 TacticNonconjugatedDieneCyclopolymerizationand
Cyclocopolymerization............................................................. 489
IlKim
Chapter20 StereochemistryofPolymersFormedbyMetathesisPolymerizationof
BicyclicandPolycyclicOlefins.................................................... 509
DarraghBreen,KatherineCurran,andWilhelmRisse
Chapter21 StereoregularityofPolyacetyleneandItsDerivatives ............................ 553
ToshioMasuda,MasashiShiotsuki,andJunichiTabei
V FunctionalandNon-OlefinicMonomers ............................................. 575
Chapter22 TacticityinEthylene/CarbonMonoxide/VinylCo-and
Terpolymerizations.................................................................. 577
KyokoNozaki
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Chapter23 StereoselectiveAcrylatePolymerization........................................... 593
EdwardL.MarshallandVernonC.Gibson
Chapter24 DiscreteCatalystsforStereoselectiveEpoxidePolymerization.................. 627
HiroharuAjiro,ScottD.Allen,andGeoffreyW.Coates
Chapter25 StereoselectivePolymerizationofLactide......................................... 645
MalcolmH.ChisholmandZhipingZhou
Glossary............................................................................................ 661
Index................................................................................................ 667
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Preface
Polymersareoneofthemodernworld’smostintriguingandversatilematerials,abletoassumeanear-
infinitevarietyofshapesandpropertiesthatpermeatealmosteveryaspectofourlivesasconsumers.
Thecommutativenatureofplasticsisnotonlyafunctionoftheirmelt-processingcapabilities,butalso
areflectionofthewidevarietyofpossiblemicrostructuresthateachpolymerchain(ordistribution
ofchains)canassumeasauniquefingerprintofthepolymerizationmechanism.
Among the many aspects of polymer chain microstructures, tacticity is arguably the most
critical for determining polymer properties and uses. For example, atactic polypropylene is a
soft, amorphous material, useful only in very limited applications such as adhesives or asphalt
modifiers, while isotactic polypropylene is stiff and highly crystalline, possessing good heat res-
istance and a high melting point. Isotactic polypropylene is one of today’s most commercially
important polymers, used to make a wide range of products including fibers, food containers,
molded auto parts, films, and nonwoven fabrics. These significant property differences arise
principallyfromalignmentofthepolymer’spendantmethylgroupsintoaregularratherthanrandom
arrangement.
Today, the development of a new polymeric material requires a keen understanding of how
to manipulate the most intimate features of individual polymer chains—tacticity, branching,
comonomersequencedistribution,blocklength,regioerrors—toobtaindesirablephysicalproperties
andperformance.Themodernpolymerchemistmustpossessagoodunderstandingoffundamental
microstructuralstructure–propertyrelationshipsforanysystemunderstudy,bothfromthesynthetic
perspective(relationshipsbetweenpolymerizationcatalystligand/activesitestructure,polymeriza-
tionmechanism,andchainmicrostructure)andtheperformanceperspective(relationshipsbetween
chainmicrostructure,phasebehavior,andbulkproperties).
With this book, we have sought to create a one-volume reference containing information
on the most important classes of tactic polymers and polymerizations carried out using single-
site catalysis.1−5 This book contains 25 individual review chapters on tactic polymers and
polymerizations,eachcontributedbytopresearchersinthearea,groupedintofiveparts.
Thefirstpartdescribesthebasictypesoftacticpolypropylenesandcatalystsystemsusedtopre-
parethem.Thesechaptersprovidethereaderwithanoverviewofknowncatalyststructure–polymer
propertyrelationships,andexplainthecriticalligandmodificationstrategiesusedtoachievestereo-
control. Newer classes of polypropylene polymerization catalysts, including nonmetallocene and
latetransitionmetalprecatalysts,arealsohighlightedinordertoexemplifyemergingcatalystdesign
techniques.Achapter discussing theoretical site-control studies is included to illustrate how such
techniquesassistwithandcomplementcatalystdesign.Introductionstothefundamentalconceptsof
tacticityandpolymerizationmechanismsarealsofeaturedintheearliestchapters.Thesecondpart
containschaptershighlightingtheroleoftacticityinthedesignofpolypropyleneswithspecialphys-
icalproperties(stereoblock,elastomeric,andfunctionaltacticmaterials).Tacticityconsiderationsin
ethylene–propylenecopolymersarealsoexamined.
Inthethirdpart,tacticityconsiderationsareexpandedtoothermonoolefinicmonomersandpoly-
mers,withchapterscoveringtacticα-olefinandstyrenepolymerizations.Ditacticpolymerizations
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