Handbook of Metathesis v3: Polymer Synthesis

424 Pages·2015·6.915 MB·English

by  Robert H. Grubbs, Ezat Khosravi

EditedbyRobertH.Grubbs
andEzatKhosravi
HandbookofMetathesis
Volume3:
PolymerSynthesis

EditedbyRobertH.GrubbsandEzatKhosravi
Handbook of Metathesis
Volume3:PolymerSynthesis
SecondEdition
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V
Contents
Preface XIII
ListofContributors XV
1 SynthesisofHomopolymersandCopolymers 1
ChristianSlugovc
1.1 Introduction 1
1.2 Initiators 2
1.3 Monomers 5
1.4 SynthesisofPolymerswithComplexArchitectures 9
1.5 StereochemistryandSequenceControlinROMP 15
1.6 Conclusion 16
References 16
2 ROMPinDispersedMedia 25
ValérieHéroguez,AbrahamChemtoband
DamienQuemener
2.1 Introduction 25
2.2 EmulsionROMP 25
2.2.1 Mini-emulsionROMP 27
2.2.2 Micro-emulsionROMP 28
2.2.3 MicellarROMP 30
2.2.4 ROMPinNonaqueousEmulsions 30
2.3 DispersionROMP 31
2.3.1 BiomedicalApplicationsofPNBE–PEOCore–Shell
Nanoparticles 32
2.4 SuspensionROMP 35
2.5 FormationofNanoparticles 36
2.5.1 PhotoactiveROMPAssemblies 39
2.5.2 Miscellaneous 41
2.6 Conclusion 42
References 42
VI Contents
3 TelechelicPolymers 45
NilsHanikandAndreasF.M.Kilbinger
3.1 Introduction 45
3.2 Mono-telechelicPolymers 47
3.2.1 ReactionwithSubstitutedVinylEthers 47
3.2.2 VinylLactoneQuenching 48
3.2.3 TerminalCrossMetathesis 48
3.2.3.1 UsingSymmetricalOlefins 48
3.2.3.2 UsingAsymmetricalOlefins 51
3.2.4 ReactionwithOxygen 51
3.2.5 SacrificialDiblockCopolymerSynthesis 51
3.2.6 CatalystPrefunctionalization 53
3.2.6.1 FunctionalCatalystsfromPrecursorComplexes 53
3.2.6.2 FunctionalCatalystsviaCrossMetathesis 53
3.2.7 AldehydeQuenching 54
3.3 Homo-telechelicPolymers 55
3.3.1 DegradationofUnsaturatedPolymersandADMET
Polymerization 56
3.3.2 ROMP/ChainTransfer 58
3.3.3 SacrificialMultiblockCopolymers 63
3.4 Hetero-telechelicPolymers 64
3.4.1 PrefunctionalizationwithFunctionalAlkylideneInitiators 64
3.4.2 PrefunctionalizationwithSacrificialSynthesis 64
3.5 ConclusionsandOutlook 66
Acknowledgments 66
References 67
4 SupramolecularPolymers 71
ElizabethElacqua,NielstenBrummelhuis,andMarcusWeck
4.1 Introduction 71
4.2 Main-ChainSupramolecularPolymers 73
4.2.1 Macromonomers 73
4.2.2 ABCTriblockCopolymers 75
4.3 Side-Chain-FunctionalizedSupramolecularPolymers 77
4.3.1 Hydrogen-BondingRecognitionMotifs 77
4.3.2 MetalCoordination-BasedRecognitionMotifs 84
4.3.3 MixedOrthogonalRecognitionMotifs 86
4.4 SupramolecularArchitecturesbyDesign 88
4.5 Conclusion 89
References 90
5 SynthesisofMaterialswithNanostructuredPeriodicity 93
GarretM.Miyake,RaymondA.Weitekamp,andRobertH.Grubbs
5.1 Introduction 93
5.2 SequentialROMP 94
Contents VII
5.3 InorganicCompositeMaterials 96
5.4 ABATriblockCopolymers 98
5.5 NanostructureswithDomainSizesExceeding100nm 101
5.6 Conclusions 111
References 111
6 SynthesisofNanoparticles 115
AnthonyM.Rush,CarrieR.James,andNathanC.Gianneschi
6.1 Introduction 115
6.2 FormationofNanoparticles 116
6.3 SynthesisviaGrafting-throughApproach 117
6.4 SynthesisviaGrafting-toApproach 134
6.4.1 Grafting-toPolymerBackbonesviaanActivatedEster 135
6.4.2 Grafting-toPolymerBackbonesviaCopper-CatalyzedClick
Reaction 140
6.5 SynthesisviaGrafting-fromApproach 141
6.6 Summary 144
References 145
7 SynthesisofBiodegradableCopolymers 149
IzabelaCzelusniakandEzatKhosravi
7.1 Introduction 149
7.2 Polyester-FunctionalizedPolymers 150
7.3 Peptide-FunctionalizedPolymers 152
7.4 Carbohydrate-FunctionalizedPolymers 154
7.5 AntimicrobialPolymers 156
7.6 PolymericBetaines 157
7.7 ROMPPolymersasDrugCarriers 158
7.8 ROMPPolymersforTissueScaffolds 161
7.9 Conclusion 164
References 164
8 BiologicallyActivePolymers 169
LauraL.KiesslingandJoshuaM.Fishman
8.1 Introduction 169
8.2 BenefitsofROMPforBioactivePolymerSynthesis 170
8.3 BiologicallyActivePolymericDisplays 170
8.3.1 CatalystDesign 171
8.3.2 MonomerDesignforBioactivePolymers 172
8.3.3 TroubleshootinginPolymerizationofBioactiveMonomers 173
8.3.4 RoutestoFunctionalizedPolymers 175
8.4 ExploitingtheBulkPropertiesofPolymers 177
8.4.1 Hydrogels 177
8.4.2 Coatings 178
8.4.2.1 NonfoulingSurfaces 178
VIII Contents
8.4.2.2 AntimicrobialPeptides 179
8.4.2.3 Integrin-BindingMaterialsforCellAdhesionand
Spreading 181
8.4.2.4 Biolubricants 182
8.4.3 DrugDelivery 183
8.4.3.1 Self-AssembledPolymerNanoparticles 183
8.4.3.2 BottlebrushROMPPolymers 184
8.4.4 AnalyticalToolsforBiodetection 185
8.4.4.1 On-ChipAssays 185
8.4.4.2 ImagingAgents 187
8.5 ProbesofBiologicalProcesses 188
8.5.1 Inhibitors 189
8.5.1.1 TheSelectinsandtheInflammatoryResponse 189
8.5.1.2 IntegrinsandCellularAdhesion 190
8.5.1.3 GAGSurrogates 192
8.5.2 Effectors 192
8.5.2.1 Chemotaxis 193
8.5.2.2 MultivalentAntigensinB-CellSignaling 193
8.5.3 CellPenetrationPolymers 195
8.5.3.1 TranslocationDomainsandPolyplexes 195
8.5.3.2 TargetedDelivery:BCellInternalization 196
8.5.4 AssemblingMultiproteinComplexes 197
8.5.4.1 RegulationofImmuneResponses 198
8.6 Outlook 198
References 199
9 CombinationofOlefinMetathesisPolymerizationwithClick
Chemistry 207
SteffenKurzhalsandWolfgangH.Binder
9.1 Introduction 207
9.2 AttachingFunctionalGroupsforClickReaction 208
9.2.1 Alkyne(s) 209
9.2.2 Azide(s) 210
9.2.3 Thiol(s) 211
9.2.4 Acrylate(s)/Maleimide(s) 212
9.2.5 Anthracene(s) 212
9.2.6 ClickReactionbeforeROMP 212
9.3 Copper-CatalyzedAzide/AlkyneClickReaction 213
9.3.1 PolymerswithHydrogen-BondingMotifs 213
9.3.2 BiomedicalApplications 215
9.3.3 ComplexPolymericArchitecturesviaAzide/AlkyneClick
Chemistry 216
9.3.4 Grafting-fromandCatalystDesign 218
9.4 Diels–AlderClickReaction 219