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Functional Polymers by Post-Polymerization Modification Concepts, Guidelines and Applications

by: Theato, Patrick; Klok, Harm-anton

Functional Polymers by Post-Polymerization Modification Concepts, Guidelines and Applications

by: Theato, Patrick; Klok, Harm-anton

ISBN 13:
9783527331154
ISBN 10:
3527331158
Edition: 1st
Format: Hardcover
Copyright: 12/26/2012
Publisher: Wiley-VCH

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Functional Polymers by Post-Polymerization Modification Concepts, Guidelines and Applications > ISBN13: 9783527331154

Summary

Filling the gap for a book dealing with synthetic strategies and recent developments, this volume provides a comprehensive and up-to-date overview of the field of post-polymerization modification. As such, the international team of expert authors covers a wide range of topics, including new synthetic techniques utilizing different reactive groups for post-polymerization modifications of synthetic polymers, as well as modification of biomimetic and biological polymers. Furthermore, industrial applications of polymers that are synthesized by post-polymerization techniques and experimental procedures are included. With its experimental section this is an indispensable reference for the daily lab work of polymer chemists in both academia and industry researching the field of polymer synthesis.

Author Biography

Patrick Theato is Associate Professor for polymer chemistry at the University of Hamburg. He studied chemistry at Mainz (Germany) and Amherst (USA), and received his Ph.D. in 2001 from the University of Mainz with Prof. R. Zentel. After postdoctoral research with Prof.
D.Y. Yoon (Seoul National University, Korea) and Prof. C.W.. Frank (Stanford University, USA), he joined the University of Mainz as a young faculty member and completed his Habilitation in 2007. From 2009 to 2012 he held a joint appointment with the School of Chemical and Biological Engineering at Seoul National University within the World Class University program. In 2011 he accepted a prize senior lectureship at the University of Sheffield, UK. Shortly after he moved to University of Hamburg, Germany. He serves as an Editorial Advisory Board Member of "Macromolecules". His current research interests include the defined synthesis of reactive polymers, block copolymers, design of multi stimuli-responsive polymers, versatile functionalization of interfaces, hybrid polymers, polymers for electronics and templating of polymers.

Harm-Anton Klok is Full Professor at the Institutes of Materials and Chemical Sciences and Engineering at the Ecole Polytechnique F?d?rale de Lausanne (EPFL) (Switzerland). He received his Ph.D. in 1997 from the University of Ulm (Germany) after working with Prof. M. M?ller. After postdoctoral research with Prof. D. N. Reinhoudt (University of Twente) and Prof. S. I. Stupp (University of Illinois at Urbana-Champaign, USA), he joined the Max Planck Institute for Polymer Research in Mainz (Germany) in early 1999 as a project leader in the group of Prof. K. M?llen. In November 2002, he was appointed to the faculty of EPFL. Harm-Anton Klok is recipient of the 2007Arthur K. Doolittle Award of the American Chemical Society (ACS) and is Associate Editor of the ACS journal "Biomacromolecules".

List of Abbreviations XIII

List of Contributors XIX

1 History of Post-polymerization Modification 1
Kemal Arda G¨unay, Patrick Th´eato, and Harm-Anton Klok

1.1 Introduction 1

1.2 Post-polymerization Modification via Thiol-ene Addition 3

1.3 Post-polymerization Modification of Epoxides, Anhydrides, Oxazolines, and Isocyanates 4

1.4 Post-polymerization Modification of Active Esters 13

1.5 Post-polymerization Modification via Thiol-Disulfide Exchange 19

1.6 Post-polymerization Modification via Diels-Alder Reactions 20

1.7 Post-polymerization Modification via Michael-Type Addition 22

1.8 Post-polymerization Modification via Azide Alkyne Cycloaddition Reactions 27

1.9 Post-polymerization Modification of Ketones and Aldehydes 32

1.10 Post-polymerization Modifications via Other Highly Efficient Reactions 35

1.11 Concluding Remarks 39

References 39

2 Post-polymerization Modifications via Active Esters 45
Ryohei Kakuchi and Patrick Theato

2.1 Introduction 45

2.2 Active Esters in the Side Group 46

2.2.1 Homopolymers 47

2.2.1.1 General 47

2.2.1.2 Stimuli-Responsive Polymers 48

2.2.1.3 Biologically Active Polymers 49

2.2.1.4 Thin Films 51

2.2.1.5 Polymeric Ligands for Nanoparticles 52

2.2.1.6 Miscellaneous Uses of Active Ester Polymers 53

2.2.2 Block Copolymers 53

2.2.2.1 General 53

2.2.2.2 Block Copolymers and Inorganic Moieties 53

2.2.2.3 Amphiphilic Block Copolymers 54

2.2.2.4 Stimuli-Responsive Block Copolymers 54

2.3 Star Polymers 55

2.4 Active Esters at the End Groups 55

2.5 Controlled Positioning of Active Ester Moieties 57

2.6 Summary 58

References 59

3 Thiol–ene Based Functionalization of Polymers 65
Nikhil K. Singha and Helmut Schlaad

3.1 Introduction 65

3.2 General Considerations and Mechanisms 66

3.2.1 Radical Thiol–ene Addition 66

3.2.2 Nucleophilic Thiol–ene Addition 68

3.3 Functionalization of Polymers 69

3.3.1 Endfunctionalization 69

3.3.1.1 Polymer–ene/Thiol 70

3.3.1.2 Polymer–SH/Olefin 72

3.3.2 Polymer-Analog Reactions 75

3.3.2.1 Polyene/Thiol 75

3.3.2.2 Polythiol/Olefin 80

3.3.3 Bioconjugation 81

3.4 Summary 83

Acknowledgments 83

References 84

4 Thiol–yne Chemistry in Polymer and Materials Science 87
Andrew B. Lowe and Justin W. Chan

4.1 Introduction 87

4.2 The Thiol–yne Reaction in Small-Molecule Chemistry 88

4.3 The Thiol–yne Reaction in Polymer and Material Synthesis 95

4.3.1 Network Polymers 96

4.3.2 Surface-Initiated Polymerizations and Modifications 98

4.3.3 Polymer Beads 103

4.3.4 Hyperbranched Polymers 104

4.3.5 Dendrimers and Dendritic Polymers 108

4.3.6 Main chain α- and ω-Functional (co)Polymers 110

4.3.7 Nonradical Thiol–yne Click Polymerization 114

4.3.8 Summary and Outlook 115

References 116

5 Design and Synthesis of Maleimide Group Containing Polymeric Materials via the Diels-lder/Retro Diels-Alder Strategy 119
Tugce Nihal Gevrek, Mehmet Arslan, and Amitav Sanyal

5.1 Introduction 119

5.2 Maleimide Functional Group Containing Polymeric Materials 120

5.3 The Diels-Alder/Retro Diels-Alder Cycloaddition-Cycloreversion Reactions 120

5.4 Application of Diels-Alder/Retro Diels-Alder Reaction to Synthesize Maleimide-Containing Polymers 122

5.4.1 Synthesis of Polymers Containing the Maleimide Group at the Chain Termini 122

5.4.2 Polymers Containing Maleimide Groups as Side Chains 141

5.4.3 Synthesis of Maleimide-Containing Hydrogels Obtained Using the Diels–Alder/Retro Diels–Alder Reaction-Based Strategy 147

5.5 Conclusions 150

References 150

6 The Synthesis of End-Functional Ring-Opening Metathesis Polymers 153
Andreas F. M. Kilbinger

6.1 Introduction 153

6.2 End-Functionalization Methods in General 156

6.3 Functionalization during Initiation 159

6.4 Functionalization after Propagation 160

6.4.1 Reaction with Carbonyl Groups 161

6.4.2 Reaction with Molecular Oxygen 162

6.4.3 Reaction with Functional Vinyl Ethers 162

6.4.4 Reaction with Functional Vinyl Esters 163

6.4.5 Reaction with Nondeactivating Olefins 165

6.5 Functionalization during Propagation 166

6.5.1 Using Chain-Transfer Agents 166

6.5.2 Sacrificial Synthesis 167

6.6 Conclusions and Outlook 168

Acknowledgments 168

References 169

7 Functional Polymers with Controlled Microstructure Based on Styrene and N-Substituted Maleimides 173
Delphine Chan-Seng, Mirela Zamfir, and Jean-Fran¸cois Lutz

7.1 Introduction 173

7.2 Background on Radical Copolymerization of Styrene and Maleimides 174

7.2.1 Conventional Radical Polymerization 175

7.2.2 Controlled Radical Polymerization 177

7.3 Precise Incorporation of Maleimide Units on Polystyrene Backbone 179

7.3.1 Strategy 179

7.3.2 Maleimides 180

7.3.3 Styrene Derivatives 181

7.4 Tuning a Simple Technique for the Preparation of Sequence-Controlled Polymers to the Elaboration of Functionalized Well-Defined Macromolecules 182

7.4.1 Incorporation of Different Functionalities on the Same Polymer Backbone of a Well-Defined Polymer Possessing a Controlled Microstructure 183

7.4.2 Designing 1D Periodic Molecular Arrays 183

7.4.3 Elaboration of New Materials by Post-polymerization Modification 185

7.4.3.1 Activated Esters as Precursor of Post-polymerization Modification 186

7.4.3.2 Formation of Positionable Covalent Bridges 186

7.5 Summary and Outlook 189

References 189

8 Temperature-Triggered Functionalization of Polymers 193
Bongjin Moon

8.1 Introduction 193

8.2 Temperature-Triggered Alteration of Polymer Property 194

8.2.1 Thermolysis of t-Butyl Esters, Carbonates, and Carbamates 194

8.2.2 Thermolysis of Miscellaneous Esters, Carbonates, and Carbamates 197

8.2.3 Thermolysis of Acetals 199

8.3 Temperature-Triggered Generation of Reactive Groups 201

8.3.1 Thermolytic Generation of Anhydride Group in Polymers 201

8.3.2 Thermolytic Generation of Ketenes in Polymers 206

8.3.3 Thermolytic Generation of Transient Reactive Groups 211

8.4 Conclusions 213

References 215

9 New Functional Polymers Using Host–Guest Chemistry 217
Ryosuke Sakai and Toyoji Kakuchi

9.1 Introduction 217

9.2 Polymers with Responsive Three-Dimensional Structures 218

9.2.1 Helicity Induction 218

9.2.2 Helix Inversion 220

9.3 Polymer Probes for Specific Chemical Sensing 222

9.3.1 Colorimetric Probes 222

9.3.2 Fluorescent Probes 226

9.4 Responsive Soft Materials 228

9.4.1 Responsive Smart Gels 228

9.4.2 Thermoresponsive Materials with Molecular Recognition Ability 230

9.5 Functional Polyrotaxanes 232

References 234

10 Glycopolymers via Post-polymerization Modification Techniques 237
James A. Burns, Matthew I. Gibson, and C. Remzi Becer

10.1 Introduction 237

10.2 Synthesis and Controlled Polymerization of Glycomonomers 238

10.3 Post-polymerization Modification of Polymer Scaffolds to Synthesize Glycopolymers 240

10.4 Azide–Alkyne Click Reactions 243

10.5 Utilizing Thiol-Based Click Reactions 252

10.6 Thiol–ene Click Reactions 253

10.7 Thiol–yne Click Reactions 254

10.8 Thiol–Halogen Substitution Reactions 255

10.9 Alkyne/Alkene Glycosides: ‘‘Backward’’ Click Reactions 258

10.10 Post-polymerization Glycosylation of Nonvinyl Backbone Polymers 259

10.11 Conclusions and Outlook 260

Acknowledgments 262

References 262

11 Design of Polyvalent Polymer Therapeutics 267
Jacob T. Martin and Ravi S. Kane

11.1 Introduction 267

11.2 Polyvalent Polymer Therapeutics 268

11.2.1 Polymer Micelles 269

11.2.2 Controlled-Molecular-Weight Linear Polymers 273

11.2.3 Controlled Ligand Spacing 276

11.2.4 Matching Valency to the Target 280

11.2.5 Biocompatible Polymer Scaffolds 284

11.2.6 Bioengineered Polymer Scaffolds 285

11.3 Conclusions 287

References 288

12 Posttranslational Modification of Proteins Incorporating Nonnatural Amino Acids 291
Haresh More, Ching-Yao Yang, and Jin Kim Montclare

12.1 Posttranslational Modification of Existing Amino Acids within Protein Chain 291

12.1.1 Phosphorylation 291

12.1.2 Acetylation 292

12.1.3 Methylation 292

12.1.4 Glycosylation 293

12.1.5 Hydroxylation 293

12.1.6 Sulfation 294

12.2 Exploiting Biosynthetic Machinery: Cotranslational Approach 294

12.2.1 Site-Specific Incorporation (SSI) 294

12.2.1.1 In vitro SSI 294

12.2.1.2 In vivo SSI 298

12.2.1.3 Applications 306

12.2.2 Residue-Specific Incorporation (RSI) 308

12.2.2.1 Endogenous AARS 310

12.2.2.2 Overexpression of Endogenous AARS 310

12.2.2.3 Shrinking the AARS Editing Pocket 311

12.2.2.4 Enlarging the AARS Binding Pocket 312

12.2.2.5 Applications 312

12.3 Intein-Inspired Ligation Approach 315

12.3.1 Native Chemical Ligation (NCL) 316

12.3.1.1 Sulfur-Based N-Terminal Residue 316

12.3.1.2 Selenocysteine-Based N-Terminal Residue 316

12.3.2 Expressed Protein Ligation (EPL) 318

12.4 Combined Approach 319

12.4.1 RSI and EPL 319

12.4.2 SSI and Intein-Mediated Ligation 319

12.5 Protein and Polymer Conjugates 320

12.5.1 PEGlyation of Proteins via NAA 321

12.6 Modulating the Physicochemical Properties of Protein Polymers via NAA Incorporation 322

12.7 Future in Combined Technologies to Fabricate Tailored Protein-Polymer Conjugates as New Materials 322

12.8 Conclusion and Future Perspectives 323

Acknowledgments 324

References 324

13 Functionalization of Porous Polymers from High-Internal-Phase Emulsions and Their Applications 333
Linda Kircher, Patrick Theato, and Neil R. Cameron

13.1 Introduction 333

13.1.1 Preparation Method of polyHIPEs 334

13.2 Functionalization of polyHIPEs 335

13.2.1 Functionalization of polyHIPEs Based on Copolymerization with Functional Comonomers 337

13.2.2 Functionalization of polyHIPEs by Post-polymerization Modification 342

13.2.3 Functionalization of polyHIPEs Based on Grafting Modification of Porous Materials 343

13.2.3.1 ATRP to Functionalize polyHIPEs 345

13.2.4 Click Chemistry for Functionalization of polyHIPEs 346

13.2.5 Thiol-ene-based polyHIPEs 347

13.2.6 Dicyclopentadiene polyHIPEs 347

13.3 Applications 347

13.3.1 Tissue Engineering 348

13.3.2 Support Materials 348

13.4 Conclusions 349

References 350

14 Post-polymerization Modification of Polymer Brushes 353
Sara Orski, Gareth Sheppard, Rachelle Arnold, Joe Grubbs, and Jason Locklin

14.1 Introduction 353

14.2 Synthesis and Strategies for Functional Polymer Brushes 357

14.2.1 Preparation of Active Ester Polymer Brushes by SI-ATRP 357

14.2.2 Synthesis of Poly(NHS4VB) Block Copolymer Brushes with 2-Hydroxyethyl Acrylate, tert-Butyl Acrylate, or Styrene 360

14.2.3 Functionalization of Poly(NHS4VB) Brushes with Primary Amines 360

14.2.4 Quantification of Active Ester Post-polymerization Modification 361

14.3 Applications of Polymer Brush Modification: Multifunctional Surfaces via Photopatterning 362

14.3.1 Polymer Brush Functionalization with Photoactivated Dibenzocyclooctyne for Catalyst-Free Azide Cycloaddition 362

14.3.2 Copper-Free Click of Dibenzocyclooctyne and Azido-FL/Azido-RB 365

14.4 Conclusions and Future Outlook 366

References 366

15 Covalent Layer-by-Layer Assembly Using Reactive Polymers 371
Adam H. Broderick and David M. Lynn

15.1 Introduction 371

15.2 Overview of Layer-by-Layer Assembly: Conventional versus Covalent Assembly 371

15.3 Scope and Organization 375

15.4 Covalent LbL Assembly Based on ‘‘Click Chemistry’’ 375

15.5 Reactive LbL Assembly Using Azlactone-Functionalized Polymers 387

15.6 Other Reactions and Other Approaches 396

15.7 Concluding Remarks 401

Acknowledgments 402

References 402

Index 407

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