Complex Macromolecular Architectures: Synthesis, Characterization, and Self-Assembly

834 Pages·2011·13.28 MB·English

by  Nikos Hadjichristidis

COMPLEX
MACROMOLECULAR
ARCHITECTURES
Complex Macromolecular Architectures: Synthesis, Characterization, and Self-Assembly, First Edition.
Edited by Nikos Hadjichristidis, Akira Hirao, Yasuyuki Tezuka and Filip Du Prez.
© 2011 John Wiley & Sons (Asia) Pte Ltd. Published 2011 by John Wiley & Sons (Asia) Pte Ltd. ISBN: 978-0-470-82513-6
COMPLEX
MACROMOLECULAR
ARCHITECTURES
SYNTHESIS, CHARACTERIZATION,
AND SELF-ASSEMBLY
Editors
Nikos Hadjichristidis
University ofAthens, Greece
Akira Hirao
Tokyo Instituteof Technology, Japan
Yasuyuki Tezuka
Tokyo Instituteof Technology, Japan
Filip Du Prez
Ghent University, Belgium
Thiseditionfirstpublished2011
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LibraryofCongressCataloging-in-PublicationData
Complexmacromoleculararchitectures:synthesis,characterization,andself-assembly/Nikos
Hadjichristidis...[etal.].
p.cm.
Includesbibliographicalreferencesandindex.
ISBN978-0-470-82513-6(hardback)
1. Macromolecules.2. Polymerization. I.Hadjichristidis,Nikos,1943-
QD381.C6582011
5470.7–dc22
2010053511
PrintISBN:978-0-470-82513-6
ePDFISBN:978-0-470-82514-3
oBookISBN:978-0-470-82515-0
ePubISBN:978-0-470-82827-4
Setin10/12ptTimesbyThomsonDigital,Noida,India
Contents
List of Contributors xvii
Preface xix
About the Editors xxi
PART ONE SYNTHESIS 1
1 Cyclicand Multicyclic Topological Polymers 3
Takuya Yamamoto and YasuyukiTezuka
1.1 Introduction 3
1.2 The Progress on the SynthesisofRing Polymers 4
1.2.1 Ring-Expansion Polymerization 4
1.2.2 Cyclizationby Telechelic Polymer Precursors 6
1.3 Functional Ring Polymers andTopology Effects Thereby 9
1.3.1 Polymer Catenanes Using a Ring Polymer Precursor
Havingan H-Bonding Unit 9
1.3.2 Single-MoleculeSpectroscopy Using aRing Polymer
Havinga Chromophore Unit 10
1.3.3 Crystallization Dynamics Using a Defect-Free RingPolymer 12
1.4 NewDevelopmentsintheConstructionofMulticyclicPolymerTopologies 13
1.4.1 Fused MulticyclicPolymers 14
1.4.2 SpiroMulticyclic Polymers 15
1.4.3 BridgedMulticyclic Polymers 17
1.5 Conclusions and Perspectives 17
References 17
2 Ultrarapid Approaches to Mild Macromolecular Conjugation 21
AndrewJ.Inglis andChristopherBarner-Kowollik
2.1 Introduction 21
2.2 RAFT-HDAChemistry 23
2.3 Ultrafast RAFT-HDAChemistry 25
2.4 Cycloadditionswith Strainedor Activated Alkynes 27
2.5 Thiol-Ene/Thiol-Yne Chemistry 33
vi Contents
2.6 Thiol-Isocyanate Chemistry 36
2.7 Thio-Bromo Chemistry 40
2.8 InverseElectron Demand Diels–Alder 42
2.9 Cycloadditions InvolvingNitrile Oxides 45
2.10 OximeFormation 46
2.11 Tetrazole–Ene Reaction 47
2.12 Concluding Remarks 48
References 48
3 Synthesis and Self-Assemblyof Hydrogen-Bonded
SupramolecularPolymers 53
Wolfgang H.Binder, Claudia Enders, Florian Herbst and KatharinaHackethal
3.1 Introduction 53
3.1.1 DynamicsofHydrogenBonds 55
3.1.2 Other Experimental Methods inSupramolecular Polymer Science 60
3.2 SyntheticStrategiesTowardsHydrogen-BondedSupramolecularPolymers 60
3.2.1 Carbocationic Polymerization 63
3.2.2 AnionicPolymerization 67
3.2.3 Ring-Opening Metathesis Polymerization (ROMP) 68
3.2.4 Controlled Radical Polymerization (CRP) 71
3.2.5 Polycondensation Methods 72
3.2.6 Ring-Opening Polymerization(ROP) 77
3.2.7 Other Postmodification Methods 78
3.3 Self-Assembly ofSupramolecular Polymersvia Hydrogen Bonds 78
3.3.1 Microphase-SeparatedH-BondedPolymers:TowardsPseudoblock
Copolymers 79
3.3.2 Ordering on Surfaces 82
3.3.3 Small-Molecule Ordering into Polymersvia H Bonds 82
3.3.4 Applications of H-Bonded Supramolecular Polymers 86
3.4 Conclusions and Outlook 86
Acknowledgment 87
References 87
4 RecentSyntheticDevelopmentsinMiktoarmStarPolymerswithMorethan
ThreeDifferentArms 97
AkiraHirao,Mayumi Hayashi, Tomoya Higashiharaand Nikos Hadjichristidis
4.1 Introduction 97
4.2 Miktoarm Star-Branched Polymers up to2000 98
4.3 Novel and Versatile Methodology Based on an“IterativeApproach” for
Miktoarm Star Polymer Syntheses 102
4.3.1 IterativeMethodology with Regeneration of DPE Function 102
4.3.2 IterativeMethodology with Regeneration of Two orMore DPE
Functions 104
4.3.3 IterativeMethodology with Regeneration of 1,3-Butadiene
Function 111
4.3.4 IterativeMethodology with Regeneration of Benzyl Bromide
Function 113
Contents vii
4.3.5 Convergent Synthesis ofMiktoarm Star-Branched Polymers
Using Polymer Anions 116
4.4 Miktoarm Star Polymersby Other Methodologies Based on Living
AnionicPolymerization 119
4.5 Miktoarm Star Polymersby Living/Controlled Radical Polymerization 123
4.5.1 ABC Miktoarm Star Polymers 123
4.5.2 ABCD MiktoarmStar Polymers 125
4.6 Concluding Remarks 127
References 128
5 PreciseSynthesisofDendrimer-LikeStar-BranchedPolymers,aNewClass
of Well-Defined Hyperbranched Polymers 133
Hee-Soo Yoo and AkiraHirao
5.1 Introduction 133
5.2 SyntheticApproach 135
5.2.1 “Core-First” Divergent IterativeMethodology 135
5.2.2 “Arm-First” Convergent IterativeMethodology 142
5.2.3 “Arm-First” Divergent IterativeMethodology 147
5.3 Hydrodynamic Radii and Radii ofGyration 155
5.4 ViscosityBehavior 158
5.5 BranchingFactor(g0 Value) 160
5.6 Concluding Remarks 163
References 164
6 ArborescentPolymers with a MesoscopicScale 169
TouficNabil Aridi and Mario Gauthier
6.1 Introduction 169
6.2 Arborescent Polystyrene 171
6.2.1 Arborescent Polystyrene from Chloromethyl Coupling Sites 172
6.2.2 Arborescent Polystyrene from Acetyl Coupling Sites 173
6.2.3 One-Pot Synthesisof Arborescent Polystyrene 175
6.2.4 Physical Characterization ofArborescent Polystyrene 177
6.3 Arborescent Polystyrene-graft-Poly(2-vinylpyridine) Copolymers 179
6.3.1 Physical Characterization ofArborescent
Polystyrene-graft-Poly(2-vinylpyridine) 180
6.4 Arborescent Polystyrene-graft-Polystyrene-block-Poly
(2-vinylpyridine) 185
6.5 Arborescent Polystyrene-graft-Polyisoprene 185
6.5.1 Rheological Properties 186
6.6 Arborescent Polystyrene-graft-Poly(tert-ButylMethacrylate) 187
6.6.1 Solution Properties 188
6.7 Arborescent Polystyrene-graft-Poly(ethylene Oxide) 188
6.7.1 Self-Assembly at the Air/Water Interface 188
6.8 Arborescent Polyisoprene 191
6.9 Conclusions 192
References 193
viii Contents
7 Hyperbranched Glyco-Conjugated Polymers 195
Toshifumi Satoh and Toyoji Kakuchi
7.1 Introduction 195
7.2 Synthesis ofHyperbranchedGlyco-Conjugated Polymers 196
7.2.1 HyperbranchedPolysaccharides by Polymerization
of1,6-Anhydro-b-D-hexopyranose 196
7.2.2 HyperbranchedPolytetritol by Polymerization of
1,4-Anhydrotetritol 200
7.2.3 HyperbranchedPolytetritol by Polymerization of
2,3-Anhydrotetritol 202
7.2.4 HyperbranchedPoly(2,5-anhydro-D-glucitol) byPolymerization
of1,2:5,6-Dianhydro-D-mannitol 205
7.2.5 Hyperbranched5,6-Glucan byPolymerizationof
5,6-Anhydro-a-D-glucofuranoseDerivative 208
7.3 Unimolecular Reversed Micelle Based on Hyperbranched
Glyco-Conjugated Polymer Core 211
7.3.1 Structural Transition of Unimolecular ReversedMicelle 211
7.3.2 Biodegradable Unimolecular ReversedMicelle 216
7.3.3 pH-SensitiveUnimolecular ReversedMicellewith Size-Selective
Encapsulation Ability 219
7.4 Conclusions 225
Acknowledgments 225
References 226
8 HighlyBranched Functional Polymer Architecturesby Click-Chemistry
Strategies 229
Mieke Lammens and Filip Du Prez
8.1 Introduction 229
8.2 What’s Available inthe Click ChemistryToolbox? 230
8.3 Click Approaches for the Synthesis ofDendrimers 233
8.3.1 TraditionalSyntheticStrategies for Dendrimers 234
8.3.2 CuAAC for the Synthesis ofDendrimers 235
8.3.3 Thiol-Ene Click Chemistryfor the Synthesis ofDendrimers 236
8.3.4 [4 þ 2]Cycloaddition(Diels–Alder) Reaction for the Synthesis
ofDendrimers 240
8.4 ClickApproachesforHyperbranchedPolymers,DendronizedPolymersand
Unsymmetrical Dendrimers 241
8.4.1 Overviewof DefinitionsandTraditionalSynthetic Strategies 241
8.4.2 CuAAC for the Synthesis ofHyperbranched Polymers,
Dendronized Polymers andUnsymmetrical Dendrimers 243
8.4.3 Thiol-Yneand Thio-Bromo Chemistry for the Synthesis
ofHyperbranched Polymers 245
8.4.4 [4 þ 2]CycloadditionDiels–AlderReaction for the Synthesis
ofHyperbranched Polymersand Dendronized Polymers 247
8.5 Click Approaches for the Synthesis ofStar-Shaped Polymers 248
8.5.1 CuAAC for the Synthesis ofStar-Shaped Polymers 249
Contents ix
8.5.2 Thiol-Ene Click Chemistryfor the Synthesis
of Star-ShapedPolymers 255
8.5.3 Diels–Alder Click Reaction for the Synthesis
of Star-ShapedPolymers 258
8.6 Conclusion 260
Acknowledgments 260
References 260
9 Living Alkene Polymerization forPolyolefinArchitectures 267
Amelia M.Anderson-Wile,Joseph B. Edson and GeoffreyW.Coates
9.1 Introduction 267
9.2 Living OlefinPolymerization 268
9.2.1 Poly(1-hexene) 268
9.2.2 Polypropylene 270
9.2.3 Polyethylene 270
9.2.4 Polyolefinsfrom Conjugated Dienes,CyclicOlefinsand
Polar Monomers 270
9.2.5 Criteria for Living Polymerization 271
9.3 Early Metal OlefinPolymerization Catalysts 271
9.3.1 VanadiumAcetylacetonate Catalysts 271
9.3.2 Metallocene Catalysts 273
9.3.3 CatalystsBearingMonocyclopentadienyl-AmidoLigands 274
9.3.4 MonocyclopentadienylzirconiumAmidinate Catalysts 275
9.3.5 CatalystsBearingDiamidoLigands 280
9.3.6 Amine-Phenolate Titanium and ZirconiumCatalysts 281
9.3.7 Bis(phenoxyimine)titaniumCatalysts 284
9.3.8 Bis(phenoxyketimine)titanium Catalysts 288
9.3.9 Bis(pyrrolide-imine)titaniumCatalysts 290
9.3.10 Bis(indolide-imine)titanium Catalysts 290
9.3.11 Bis(enaminoketonato)titanium Catalysts 290
9.3.12 Bis(phosphanylphenoxide)titanium Catalysts 292
9.3.13 CatalystsSupported by sp2 andsp3 Carbon Donors 293
9.3.14 Rare-Earth Metal Catalysts 294
9.4 Late-Metal OlefinPolymerization Catalysts 295
9.4.1 Nickel and Palladiuma-Diimine Catalysts 295
9.4.2 Other Nickel Catalysts 303
9.5 Outlook andSummary 303
References 304
10 Precision Polyolefins 317
Erik B. Berda and Kenneth B. Wagener
10.1 Introduction 317
10.1.1 ADMET Polycondensation Chemistry 317
10.1.2 The EvolutionofADMET 318
10.2 Precision Polyolefins 319
10.3 LinearADMET Polyethylene:Meeting the Benchmark 321
x Contents
10.4 Precision HalogenatedPolyolefins 322
10.4.1 Synthesis ofPrecision HalogenatedPolyolefins 323
10.4.2 BehaviorofPrecision Halogenated Polyolefins 323
10.5 Precision Alkyl-Branched Polyolefins 325
10.5.1 Synthesis ofPrecision Alkyl-Branched Polyolefins 326
10.5.2 BehaviorofPrecision Alkyl-Branched Polyolefins 327
10.5.3 Increasingthe Spacing Between AlkylBranchesin Precision
Polyolefins 333
10.6 Precison Ether-Branched Polyolefins 333
10.6.1 Synthesis ofPrecise Ether-Branched Polyolefins 334
10.6.2 BehaviorofPrecise Ether-Branched Polyolefins 334
10.7 Precision Acid-Functionalized Polyolefins 335
10.7.1 Precise CarboxylicAcid Placement 335
10.7.2 Precise Phosphonic Acid andSulfonic Acid Ester Placement 337
10.8 Precision AmphiphilicCopolymers 339
10.8.1 Synthesis ofPrecision AmphiphilicCopolymers 339
10.8.2 BehaviorofPrecision Amphiphilic Copolymers 340
10.9 Summary and Outlook 343
Acknowledgments 344
References 345
11 Polyhomologation: The LivingPolymerizationof Ylides 349
Jun Luo andKennethJ.Shea
11.1 Introduction 349
11.2 Motivation for Developinga Polyethylene Surrogate 350
11.3 ALiving Polymerization ofYlides 351
11.4 Mechanism of the Polyhomologation Reaction 354
11.5 Topological Control ofPolymethylene 359
11.5.1 Postpolymerization Topological Controlof Polymethylene 359
11.5.2 Initiator-Based Topological Control 360
11.5.3 Topological Control froma Combinationof Initiator and
Postpolymerization Modification 364
11.6 Copolymers ofPolymethylene 366
11.7 Conclusion 372
Acknowledgment 373
References 373
12 Phenylenevinylene Homopolymers and Block Copolymers
via Ring-OpeningMetathesis Polymerization 377
Chin-Yang Yu and MichaelL. Turner
12.1 Introduction 377
12.2 PhenylenevinyleneHomopolymers by Ring-Opening Metathesis
Polymerization 380
12.3 PhenylenevinyleneBlock Copolymersby Ring-Opening Metathesis
Polymerization 386
12.4 Conclusions 391
References 391
Contents xi
13 Block Copolymers ContainingRod Segments 395
TomoyaHigashiharaand Mitsuru Ueda
13.1 Introduction 395
13.2 Block Copolymers ContainingNonconjugatedRod Segments 396
13.2.1 Block Copolymers Containing Polypeptide Segments 396
13.2.2 Block Copolymers Containing PolyisocyanateSegments 402
13.2.3 Block Copolymers Containing Aromatic Polyamide
Segments 404
13.3 Block Copolymers Containingp-Conjugated Rod Segments 406
13.3.1 Block Copolymers Containing Polyacetylene
Segments 406
13.3.2 Block Copolymers Containing Polyphenylene
Segments 407
13.3.3 Block Copolymers Containing Polyfluorene Segments 408
13.3.4 Block Copolymers Containing Poly(phenylenevinylene)
Segments 410
13.3.5 Block Copolymers Containing Polythiophene
Segments 412
13.4 Rod–Rod Block Copolymers 419
13.5 Concluding Remarks 421
References 422
14 Synthesis ofWell-Defined Poly(meth)acrylamides with Varied
Stereoregularity by Living Anionic Polymerization 431
Takashi Ishizone
14.1 Introduction 431
14.2 Anionic Polymerization ofN,N-Dialkylacrylamides 433
14.3 Enolates ofN,N-Dialkylamides as Novel AnionicInitiators 439
14.4 Anionic Polymerization ofProtectedN-Isopropylacrylamide 444
14.5 Anionic Polymerization ofN,N-Dialkylmethacrylamides 449
14.6 Conclusions 456
References 456
15 Complex Macromolecular Chimeras 461
Hermis Iatrou, Marinos Pitsikalis, Georgios Sakellariou
andNikos Hadjichristidis
15.1 Introduction 461
15.2 LinearMultiblock Chimeras 463
15.2.1 Primary Amine Macroinitiators 463
15.2.2 Transition-Metal ComplexMacroinitiators 468
15.3 Nonlinear Chimeras 470
15.3.1 Star Chimeras 470
15.3.2 Comb, Brush-Block, Dendritic-Like Chimeras 476
15.4 Concluding Remarks 486
References 486