Synthesis of Polymers: New Structures and Methods

1203 Pages·2012·24.278 MB·English

by  Dieter A. Schlüter, Craig Hawker, Junji Sakamoto (Eds.)

EditedbyA.DieterSchlu¨ter,
CraigJ.Hawker,and
JunjiSakamoto
SynthesisofPolymers
Volume1
RelatedTitles
Mathers,RobertT./Meier,MichaelA.R.(eds.) Mittal,Vikas(ed.)
GreenPolymerizationMethods OptimizationofPolymer
NanocompositeProperties
RenewableStartingMaterials,Catalysisand
WasteReduction
2010
Hardcover
2011
ISBN:978-3-527-32521-4
Hardcover
ISBN:978-3-527-32625-9
Matyjaszewski,K.,Mu¨ller,A.H.E.(eds.)
Knoll,Wolfgang/Advincula,RigobertoC.(eds.) ControlledandLiving
FunctionalPolymerFilms Polymerizations
2VolumeSet FromMechanismstoApplications
2011 Hardcover
Hardcover ISBN:978-3-527-32492-7
ISBN:978-3-527-32190-2
Dubois,P.,Coulembier,O.,Raquez,J.-M.(eds.)
Barner-Kowollik,Christopher/Gruendling,
Till/Falkenhagen,Jana/Weidner,Steffen(eds.) HandbookofRing-Opening
Polymerization
MassSpectrometryinPolymer
Chemistry
2009
Hardcover
2011 ISBN:978-3-527-31953-4
Hardcover
ISBN:978-3-527-32924-3
Barner-Kowollik,C.(ed.)
Harada,Akira(ed.) HandbookofRAFTPolymerization
SupramolecularPolymer
Chemistry 2008
Hardcover
ISBN:978-3-527-31924-4
2011
Hardcover
ISBN:978-3-527-32321-0
Kumar,ChallaS.S.R.(ed.)
PolymericNanomaterials
Series:NanomaterialsfortheLifeSciences
(Volume10)
2011
Hardcover
ISBN:978-3-527-32170-4
¨
Edited by A. Dieter Schluter, Craig J. Hawker, and
Junji Sakamoto
Synthesis of Polymers
New Structures and Methods
Volume 1
TheEditors AllbookspublishedbyWiley-VCHare
carefullyproduced.Nevertheless,authors,
Prof.Dr.A.DieterSchlu¨ter editors,andpublisherdonotwarrantthe
ETHZu¨rich informationcontainedinthesebooks,
DepartmentofMaterials includingthisbook,tobefreeoferrors.
Wolfgang-Pauli-Str.10 Readersareadvisedtokeepinmindthat
8093Zu¨rich statements,data,illustrations,procedural
Switzerland detailsorotheritemsmayinadvertentlybe
inaccurate.
Prof.Dr.CraigJ.Hawker
UniversityofCalifornia LibraryofCongressCardNo.:appliedfor
Chemistry&Biochemistry
3009Bldg.576(MRL) BritishLibraryCataloguing-in-Publication
SantaBarbara,CA93106 Data
USA Acataloguerecordforthisbookisavailable
fromtheBritishLibrary.
Dr.JunjiSakamoto
ETHZu¨rich Bibliographicinformationpublishedbythe
DepartmentofMaterials DeutscheNationalbibliothek
Wolfgang-Pauli-Str.10 TheDeutscheNationalbibliothek
8093Zu¨rich liststhispublicationintheDeutsche
Switzerland Nationalbibliografie;detailedbibliographic
dataareavailableontheInternetat
<http://dnb.d-nb.de>.
©2012Wiley-VCHVerlag&Co.KGaA,
Boschstr.12,69469Weinheim,Germany
Allrightsreserved(includingthoseof
translationintootherlanguages).Nopart
ofthisbookmaybereproducedinany
form–byphotoprinting,microfilm,orany
othermeans–nortransmittedortranslated
intoamachinelanguagewithoutwritten
permissionfromthepublishers.Registered
names,trademarks,etc.usedinthisbook,
evenwhennotspecificallymarkedassuch,
arenottobeconsideredunprotectedbylaw.
CoverDesign Grafik-DesignSchulz,
Fußgo¨nheim
Typesetting LaserwordsPrivateLimited,
Chennai,India
PrintingandBinding
Printedin
Printedonacid-freepaper
PrintISBN:978-3-527-32757-7
ePDFISBN:978-3-527-64409-4
oBookISBN:978-3-527-64407-0
ePubISBN:978-3-527-64408-7
MobiISBN:978-3-527-64410-0
V
Contents
ListofContributors XV
Contentof Volume1
1 Foreword 1
References 6
2 PolymerSynthesis:AnIndustrialPerspective 7
SebastianKoltzenburg
2.1 AboutthisChapter 7
2.2 Why? 8
2.3 Thesis:ThereAreNoLimitstotheFantasyofaSyntheticPolymer
Chemist 8
2.4 Antithesis:WeMayBeAbletoSynthesizeMillionsofNewPolymers
–ButWhyShouldWeDoSo? 11
2.5 Synthesis 13
2.5.1 PolymerChemistryinTwoDimensions:Coatings 13
2.5.2 PolymerChemistryGoingBroad:EffectsofMolarMass
Distribution 16
2.5.3 PolymerChemistryMeetsTheLifeSciences:PolymericDrug-Delivery
Systems 19
2.6 Conclusions 22
Acknowledgments 23
3 FromHeterogeneousZiegler–NattatoHomogeneousSingle-Center
Group4OrganometallicCatalysts:APrimerontheCoordination
PolymerizationofOlefins 25
LawrenceR.Sita
3.1 Introduction 25
3.2 ChapterProspectus 28
3.3 FundamentalsofCoordinationPolymerization 30
3.3.1 Ziegler–NattaCatalysts 30
3.3.1.1 First-GenerationZNCatalysts 31
3.3.1.2 Second-GenerationZNCatalysts 31
VI Contents
3.3.1.3 Third-GenerationZNCatalysts 32
3.3.1.4 Fourth-GenerationZNCatalysts 33
3.3.1.5 Fifth-GenerationZNCatalysts 34
3.3.2 Cossee–ArlmanMechanism 34
3.3.3 Stereocontrol 35
3.3.4 Regiocontrol 39
3.3.5 ChainTermination 40
3.3.6 MolecularWeightDistributionsandBranching 43
3.4 HomogeneousSingle-CenterCoordinationPolymerization 44
3.4.1 MolecularCatalysts 44
3.4.2 Metallocenes 44
3.4.3 Stereocontrol 46
3.4.4 StereochemicalMicrostructureAnalysis 54
3.4.5 Cocatalysts 60
3.5 Conclusions 63
Acknowledgments 63
References 63
4 Cobalt-MediatedRadicalPolymerization 67
AntoineDebuigne,RobertJe´roˆme,ChristineJe´roˆme,and
ChristopheDetrembleur
4.1 Introduction 67
4.2 MechanisticConsiderations 67
4.3 KeyParametersofCMRP 69
4.3.1 TheCobaltComplexStructure 69
4.3.2 PolymerizationConditions 71
4.4 MacromolecularEngineering 73
4.5 Cobalt-MediatedRadicalCoupling(CMRC) 75
4.6 SummaryandOutlook 76
Acknowledgments 77
References 77
5 AnionicPolymerization:RecentAdvances 81
TakashiIshizoneandAkiraHirao
5.1 Background 81
5.2 LivingAnionicPolymerizationofVariousMonomers 84
5.2.1 StyreneDerivatives 84
5.2.2 1,3-DieneMonomers 87
5.2.3 2-and4-Vinylpyridines 89
5.3 (Meth)acrylateDerivatives 90
5.4 AcrylamideDerivatives 94
5.5 CyclicMonomers 96
5.6 OtherMonomers 99
5.7 ReactionofLivingAnionicPolymerswithElectrophiles:Synthesisof
Chain-FunctionalizedPolymers 101
Contents VII
5.8 SynthesisofArchitecturalPolymersviaLivingAnionic
Polymerization 106
5.8.1 BlockCopolymers 107
5.8.2 GraftCopolymers 111
5.8.3 Star-BranchedPolymers 115
5.8.4 ComplexArchitecturalPolymers 119
5.9 AnionicPolymerization:PracticalAspects 124
5.10 ConcludingRemarks 124
References 125
6 AlkyneMetathesisPolymerization(ADIMET)andMacrocyclization
(ADIMAC) 135
AaronD.FinkeandJeffreyS.Moore
6.1 Introduction 135
6.2 CatalystDevelopment 136
6.3 Poly(PhenyleneEthynylene)sviaADIMET 138
6.4 ADIMAC-AcyclicDiyneMetathesisMacrocyclization 143
6.5 Conclusions 149
References 151
7 TheSynthesisofConjugatedPolythiophenesbyKumada
Cross-Coupling 155
FelixP.V.KochandMartinHeeney
7.1 IntroductiontoPolythiophene 155
7.2 KumadaCross-Coupling 157
7.3 PolythiophenesbyKumadaCross-Coupling 158
7.3.1 InitiationandCatalystTransferPropagation 165
7.3.2 SummaryofMechanisticStudies 172
7.3.3 InfluenceoftheCatalystonRegioregularity 174
7.3.4 Thiophene-BasedMonomers 174
7.3.5 Non-ThiopheneMonomers 184
7.3.6 EndGroupModification 186
7.4 Copolymers 188
7.4.1 RandomandAlternatingCopolymers 188
7.4.2 BlockCopolymers 190
7.5 SummaryandOutlook 193
References 194
8 ‘‘Absolute’’AsymmetricPolymerizationwithinCrystalline
Architectures:RelevancetotheOriginofHomochirality 199
IsabelleWeissbuchandMeirLahav
8.1 Introduction 199
8.2 ‘‘Through-Space’’AsymmetricPolymerizationinInclusion
ComplexesandLiquidCrystals 200
VIII Contents
8.3 IsotacticOligomersGeneratedwithinMonolayersattheAir–Water
Interface 202
8.4 ‘‘Absolute’’AsymmetricPolymerizationin3-DCrystals 207
8.4.1 ThePlanningandMaterializationofan‘‘Absolute’’Asymmetric
SynthesisofPolymers 207
8.4.2 AttemptedAmplificationofHomochirality 212
8.5 GenerationofIsotacticOligopeptidesviaPolymerizationinRacemic
Crystals 213
8.5.1 (RS)–PheNCA 214
8.5.2 (RS)-ValNCAand(RS)-LeuNCA 219
8.6 IsotacticOligopeptidesfromthePolymerizationofRacemicValNCA
orLeuNCAinAqueousSolution 222
8.7 Racemicβ-SheetsinthePolymerizationofα-Amino-Acidsin
AqueousSolutions:HomochiralOligopeptidesandCopeptidesviathe
‘‘Ehler–Orgel’’Reaction 224
8.8 IsotacticOligopeptidesfromRacemicThioestersof DL-Leuand
DL-Val 226
8.9 Conclusions 229
References 232
9 SynthesisofAbioticFoldamers 235
AnzarKhan
9.1 Introduction 235
9.2 PhenyleneEthynyleneFoldamers 237
9.2.1 BackboneFolding:DesignPrinciple 237
9.2.2 GeneralSynthesis 237
9.2.3 RepresentativeExamples 238
9.2.3.1 Oligo(meta-PhenyleneEthynylene)s(OmPEs) 238
9.2.4 Oligo(ortho-PhenyleneEthynylene)s(OoPEs) 240
9.3 HelicalAromaticAmides 241
9.3.1 BackboneFolding:DesignPrinciple 241
9.3.2 GeneralSynthesis 241
9.3.3 RepresentativeExamples 241
9.3.3.1 Oligoaryl-Dicarboxamides 241
9.3.3.2 Oligoquinoline-Dicarboxamides 244
9.3.3.3 Oligoanthranilamides 245
9.3.3.4 Oligopyridine-Dicarboxamides 245
9.4 HelicalAromaticUreas 245
9.4.1 BackboneFolding:DesignPrinciple 245
9.4.2 GeneralSynthesis 246
9.4.3 RepresentativeExamples 248
9.4.3.1 OligoheterocyclicUreas 248
9.4.3.2 OligoarylUreas 248
9.4.3.3 OligobenzoylUreas 248