Edited and written by the "Whos who" in polymer science and technology, this two-volume handbook and ready reference is a must-have compilation on the topic. At once comprehensive and trendy, all relevant topics are covered, with the chapters focusing either on the different types of polymerization reactions, or on the important classes of polymers, or on their applications. The result is an overview that equally provides a generous amount of information on the latest research developments.

A. Dieter Schl?ter is since 2004 Professor for polymer chemistry at the Materials Department of the ETH Z?rich. He studied chemistry and geophysics at the University of Munich and received in 1984 his PhD under the supervision of Prof. G. Szeimies. After post-doctoral fellowships with Prof. K. P.C. Vollhardt (UC Berkeley, USA) and Prof. W.J. Feast (University of Durham, UK) he was head of the polymer synthesis research group in Prof. G. Wegner's department at the Max-Planck-Institut f?r Polymerforschung (Mainz, Germany). 1991 he finished his habilitation, received a scholarship award of the Fonds der Chemischen Industrie and started as Professor for polymer chemistry at the
University of Karlsruhe. From 1992 to 2004 he was Full Professor at the Free University of Berlin. Since 2012 he is an elected personal member of the Swiss Academy of Engineering Sciences. His research interests are in the area of polymer synthesis with a visible component of organic chemistry.

Craig J. Hawker, FRS received his BSc (1984) degree from Queensland, Australia his PhD (1988) degree from the Cambridge (UK), followed by a post-doctoral fellowship with Professor Jean M.J. Fr?chet at Cornell from 1988 to 1990. In 2005 he moved from the IBM Almaden Research Center to the University of California, Santa Barbara where he is the Heeger Chair of Interdisciplinary Science. He is also the Director of the Materials Research Laboratory, founding Director of the Dow Materials Institute and visiting Chair Professor at King Fahd University of Petroleum and Minerals. His research activities focus on synthetic polymer chemistry and nanotechnology and has led to
more than 45 patents and over 300 papers. He has received a number of awards for his work and in 2010 he was named as a Fellow of the Royal Society.

Junji Sakamoto is currently a Habilitand at the Swiss Federal Institute of Technology (ETH) Zurich. Born in Kyoto, Japan in 1973, he studied chemistry and polymer science at Kyoto University, and earned his PhD in 2002 on the synthesis of polysaccharides under the supervision of Prof. S. Kobayashi. He carried out his postdoctoral research with Prof. K. M?llen at the Max-Planck-Institute for Polymer Research in Mainz, Germany, working on the synthesis of dendrimers (2002-2004). He then moved to the group of Prof. A.D. Schl?ter at ETH Zurich, Switzerland, working on the synthesis of macrocycles, where since 2006 he has been a group leader for 2D polymers, Suzuki polycondensation and new polymerization methodology leading to unprecedented structures.

List of Contributors XV

Content of Volume 1

1 Foreword 1

References 6

2 Polymer Synthesis: An Industrial Perspective 7
Sebastian Koltzenburg

2.1 About this Chapter 7

2.2 Why? 8

2.3 Thesis: There Are No Limits to the Fantasy of a Synthetic Polymer Chemist 8

2.4 Antithesis: We May Be Able to Synthesize Millions of New Polymers –But Why Should We Do So? 11

2.5 Synthesis 13

2.6 Conclusions 22

Acknowledgments 23

3 From Heterogeneous Ziegler–Natta to Homogeneous Single-Center Group 4 Organometallic Catalysts: A Primer on the Coordination Polymerization of Olefins 25
Lawrence R. Sita

3.1 Introduction 25

3.2 Chapter Prospectus 28

3.3 Fundamentals of Coordination Polymerization 30

3.4 Homogeneous Single-Center Coordination Polymerization 44

3.5 Conclusions 63

Acknowledgments 63

References 63

4 Cobalt-Mediated Radical Polymerization 67
Antoine Debuigne, Robert Jérôme, Christine Jérôme, and Christophe Detrembleur

4.1 Introduction 67

4.2 Mechanistic Considerations 67

4.3 Key Parameters of CMRP 69

4.4 Macromolecular Engineering 73

4.5 Cobalt-Mediated Radical Coupling (CMRC) 75

4.6 Summary and Outlook 76

Acknowledgments 77

References 77

5 Anionic Polymerization: Recent Advances 81
Takashi Ishizone and Akira Hirao

5.1 Background 81

5.2 Living Anionic Polymerization of Various Monomers 84

5.3 (Meth)acrylate Derivatives 90

5.4 Acrylamide Derivatives 94

5.5 Cyclic Monomers 96

5.6 Other Monomers 99

5.7 Reaction of Living Anionic Polymers with Electrophiles: Synthesis of Chain-Functionalized Polymers 101

5.8 Synthesis of Architectural Polymers via Living Anionic Polymerization 106

5.9 Anionic Polymerization: Practical Aspects 124

5.10 Concluding Remarks 124

References 125

6 Alkyne Metathesis Polymerization (ADIMET) and Macrocyclization (ADIMAC) 135
Aaron D. Finke and Jeffrey S. Moore

6.1 Introduction 135

6.2 Catalyst Development 136

6.3 Poly(Phenylene Ethynylene)s via ADIMET 138

6.4 ADIMAC-Acyclic Diyne Metathesis Macrocyclization 143

6.5 Conclusions 149

References 151

7 The Synthesis of Conjugated Polythiophenes by Kumada Cross-Coupling 155
Felix P. V. Koch and Martin Heeney

7.1 Introduction to Polythiophene 155

7.2 Kumada Cross-Coupling 157

7.3 Polythiophenes by Kumada Cross-Coupling 158

7.4 Copolymers 188

7.5 Summary and Outlook 193

References 194

8 ‘‘Absolute’’ Asymmetric Polymerization within Crystalline Architectures: Relevance to the Origin of Homochirality 199
Isabelle Weissbuch and Meir Lahav

8.1 Introduction 199

8.2 ‘‘Through-Space’’ Asymmetric Polymerization in Inclusion Complexes and Liquid Crystals 200

8.3 Isotactic Oligomers Generated within Monolayers at the Air–Water Interface 202

8.4 ‘‘Absolute’’ Asymmetric Polymerization in 3-D Crystals 207

8.5 Generation of Isotactic Oligopeptides via Polymerization in Racemic Crystals 213

8.6 Isotactic Oligopeptides from the Polymerization of Racemic ValNCA or LeuNCA in Aqueous Solution 222

8.7 Racemic β-Sheets in the Polymerization of α-Amino-Acids in Aqueous Solutions: Homochiral Oligopeptides and Copeptides via the ‘‘Ehler–Orgel’’ Reaction 224

8.8 Isotactic Oligopeptides from Racemic Thioesters of DL-Leu and DL-Val 226

8.9 Conclusions 229

References 232

9 Synthesis of Abiotic Foldamers 235
Anzar Khan

9.1 Introduction 235

9.2 Phenylene Ethynylene Foldamers 237

9.3 Helical Aromatic Amides 241

9.4 Helical Aromatic Ureas 245

9.5 Helical Aromatic Hydrazides 248

9.6 Heterocyclic Foldamers 249

9.7 Conclusions 257

Abbreviations 259

References 259

10 Cylindrical Polymer Brushes 263
Jiayin Yuan and Axel H. E. M¨uller

10.1 Introduction 263

10.2 Synthesis of CPBs 264

10.3 Properties of CPBs 297

10.4 CPBs as a Template for 1-D Inorganic/Hybrid Nanostructures 301

10.5 Closing Remarks 308

References 309

11 Block Copolymers by Multi-Mode Polymerizations 315
Mehmet Atilla Tasdelen and Yusuf Yagci

11.1 Introduction 315

11.2 Coupling Methods 316

11.3 Transformation Reactions 320

11.4 Dual Polymerizations 338

11.5 Conclusions 342

List of Symbols and Abbreviations 342

References 343

12 Advances in the Synthesis of Cyclic Polymers 351
Ravinder Elupula, Boyd A. Laurent, and Scott M. Grayson

12.1 Introduction 351

12.2 Bimolecular Approach 352

12.3 Unimolecular Approach 355

12.4 Ring-Expansion Approach 364

12.5 Conclusions 369

References 370

13 Cyclodehydrogenation in the Synthesis of Graphene-Type Molecules 373
Milan Kivala, Dongqing Wu, Xinliang Feng, Chen Li, and Klaus Müllen

13.1 Introduction 373

13.2 Lewis Acid-Catalyzed Oxidative Cyclodehydrogenation (Scholl Reaction) 375

13.3 Base-Induced Cyclodehydrogenation 400

13.4 Oxidative Photocyclization (Mallory Reaction) 406

13.5 Surface-Assisted Cyclodehydrogenation 409

13.6 Conclusions 415

References 416

14 Polymerizations in Micro-Reactors 421
Arend Jan Schouten

14.1 Introduction 421

14.2 Polymerization Reactions with Excess Heat Production 425

14.3 Formation of Uniform Particles 433

14.4 Scaling-Up 444

14.5 Conclusions 446

References 447

15 Miniemulsion Polymerization 449
Katharina Landfester and Daniel Crespy

15.1 Introduction 449

15.2 Radical Polymerization 450

15.3 Controlled Radical Polymerizations 457

15.4 Radiation-Induced Polymerization 457

15.5 Metal-Catalyzed Polymerizations 458

15.6 Ionic Polymerizations 459

15.7 Polyaddition 462

15.8 Polycondensation 466

15.9 Enzymatic Polymerization 466

15.10 Oxidative Polymerization 467

15.11 New Synthetic Approaches in Miniemulsion 468

15.12 Conclusions 469

References 470

16 New Conjugated Polymers and Synthetic Methods 475
Anne J. McNeil and Erica L. Lanni

16.1 Introduction 475

16.2 New Polymers Prepared via Chain-Growth Methods 476

16.3 Mechanism 478

16.4 Remaining Limitations 481

16.5 Conclusions and Outlook 482

References 483

17 Polycatenanes 487
Zhenbin Niu and Harry W. Gibson

17.1 Introduction 487

17.2 Main-Chain Polycatenanes 489

17.3 Side-Chain Polycatenanes 508

17.4 Polymeric Catenanes 515

17.5 Catenane Structures in Polymer Networks 521

17.6 Conclusions and Perspective 524

Acknowledgments 524

References 526

18 Multicyclic Polymers 531
Takuya Yamamoto and Yasuyuki Tezuka

18.1 Introduction 531

18.2 Ring Polymers with Branches (‘‘Tadpoles’’) 533

18.3 Dicyclic Polymers 534

18.4 Tricyclic and Tetracyclic Polymers 537

18.5 Oligocyclic Polymers 543

18.6 Conclusions and Perspectives 545

References 545

Content of Volume 2

19 Ring-Opening Metathesis Polymerization 547
Michael R. Buchmeiser

19.1 Introduction to Ring-Opening Metathesis Polymerization (ROMP) 547

19.2 Well-Defined Transition Metal-Based Initiators for ROMP 548

19.3 Latent Initiators for ROMP 559

19.4 ‘‘Living’’ ROMP 561

19.5 Summary and Outlook 579

References 580

20 Recent Advances in ADMET Polycondensation Chemistry 587
Erik B. Berda and Kenneth B. Wagener

20.1 Introduction 587

20.2 Functionalized Polyethylenes 588

20.3 Functional Polymers and Materials via ADMET 592

20.4 Exotic Polymer Structures 595

20.5 Summary and Outlook 598

References 598

21 Macromolecular Engineering via RAFT Chemistry: From Sequential to Modular Design 601
Christopher Barner-Kowollik, James P. Blinco, and Sébastien Perrier

21.1 Introduction 601

21.2 Sequential Design 602

21.3 Modular Design 614

21.4 Conclusions 623

References 624

22 Suzuki Polycondensation 627
Junji Sakamoto and A. Dieter Schlüter

22.1 Introduction 627

22.2 General Remarks 627

22.3 How to Perform SPC, and Aspects of Characterization 630

22.4 Recent Progress in Broadening the Scope of SPC 642

22.5 Selected Examples of Polyphenylenes and Related Polymers by SPC 651

22.6 Conclusions and Outlook 667

Acknowledgments 668

References 668

23 Enzymatic Polymerization 677
Hiroshi Uyama

23.1 Introduction 677

23.2 Enzymatic Synthesis of Phenolic Polymers 678

23.3 Enzymatic Synthesis of Polyesters 686

23.4 Concluding Remarks 695

References 696

24 Hyperbranched Polymers: Synthesis and Characterization Aspects 701
Brigitte Voit, Hartmut Komber, and Albena Lederer

24.1 Introduction 701

24.2 Synthetic Methodologies 702

24.3 Characterization Aspects 708

24.4 Separation Techniques for hb Polymers 720

24.5 Size Determination and Scaling Parameters of hb Polymers 731

24.6 Conclusions 734

References 735

25 Emulsion Polymerization 741
Hugo F. Hernandez and Klaus Tauer

25.1 Introduction 741

25.2 Molecular Description of Emulsion Polymerization 742

25.3 Radical Polymerization Kinetics in Emulsion Polymerization 746

25.4 Conclusion 770

Acknowledgments 770

References 770

26 Carbocationic Polymerization 775
Priyadarsi De and Rudolf Faust

26.1 Introduction 775

26.2 Mechanistic and Kinetic Details of Living Cationic Polymerization 776

26.3 Living Cationic Polymerization 778

26.4 Functional Polymers by Living Cationic Polymerization 786

26.5 Telechelic Polymers 790

26.6 Macromonomers 792

26.7 Linear Diblock Copolymers 796

26.8 Linear Triblock Copolymers 799

26.9 Block Copolymers with Nonlinear Architecture 801

26.10 Branched and Hyperbranched Polymers 808

26.11 Surface Initiated Polymerization – Polymer Brushes 809

26.12 Conclusions 810

References 810

27 From Star-Like to Dendrimer-Like Polymers 819
Daniel Taton

27.1 Introduction 819

27.2 Essential Features and Properties of Stars and Dendrimer-Like Polymers 820

27.3 General Methods for the Synthesis of Star Polymers 822

27.4 General Methods for the Synthesis of Dendrimer-Like Polymers 829

27.5 Conclusions 836

References 836

28 Two-Dimensional Polymers 841
Junji Sakamoto and A. Dieter Schlüter

28.1 Introduction 841

28.2 Why 2-D Polymers? 841

28.3 What Is Not Considered a 2-D Polymer? 846

28.4 General Considerations on Rational 2-D Polymer Synthesis 852

28.5 Approaches to 2-D Polymers and Related Structures 856

28.6 Conclusions and Outlook 890

Abbreviations 890

References 891

29 Poly( para-Phenylene Vinylene)s 901
Nicole Vilbrandt, Serena Nickel, Stefan Immel, Matthias Rehahn, Katja Stegmaier, Christian Melzer, and Heinz von Seggern

29.1 Introduction 901

29.2 Step-Growth Syntheses of PPVs 902

29.3 Chain-Growth Syntheses of PPVs 902

29.4 Conclusions and Outlook 916

Acknowledgments 917

References 917

30 ‘‘Click’’ Chemistry in Polymer Science: CuAAC and Thiol–Ene Coupling for the Synthesis and Functionalization of Macromolecules 923
Maxwell J. Robb and Craig J. Hawker

30.1 Introduction and Perspective 923

30.2 Polymers from ‘‘Click’’ Chemistry 926

30.3 Summary and Conclusions 964

References 965

31 Carbenes in Polymer Synthesis 973
Kyle A. Williams, Bethany M. Neilson, and Christopher W. Bielawski

31.1 Introduction to Carbenes 973

31.2 Carbenes as Structural Components of Macromolecules 975

31.3 Carbene-Based Polymerization Catalysts 991

31.4 Conclusions 1007

References 1007

32 Polymerization in Confined Geometries 1011
Takashi Uemura and Susumu Kitagawa

32.1 Introduction 1011

32.2 Polymer Synthesis in Organic Hosts 1011

32.3 Polymerization in Inorganic Hosts 1013

32.4 Polymer Synthesis in Organic–Inorganic Hybrid Hosts 1017

32.5 Summary and Conclusions 1025

References 1025

33 Accelerated Approaches to Dendrimers 1027
Marie Valèrie Walter and Michael Malkoch

33.1 Introduction 1027

33.2 Classification and Synthesis 1028

33.3 Accelerated Synthesis of Dendrimers 1030

33.4 Summary and Conclusions 1052

References 1052

34 Supramolecular Polymers 1057
Marko M. L. Nieuwenhuizen, Wilco P. J. Appel, and E. W. Meijer

34.1 Introduction 1057

34.2 Supramolecular Chemistry 1058

34.3 Supramolecular Polymerization Mechanisms 1060

34.4 Examples of Supramolecular Polymers 1061

34.5 Supramolecular Polymeric Materials 1077

34.6 Future Perspectives 1083

References 1085

35 Nucleic Acid Polymers and DNA Synthetic Polymer Hybrid Materials Generated by Molecular Biology Techniques 1089
Minseok Kwak and Andreas Herrmann

35.1 Introduction 1089

35.2 DNA Hydrogels Mediated by the Action of DNA Ligases 1091

35.3 DNA Block Copolymers and DNA Networks Generated by the Polymerase Chain Reaction 1093

35.4 Generating DNA–Synthetic Polymer Hybrids with DNA Polymerases 1100

35.5 Plasmids and Catenated Nucleic Acid Architectures from Circular DNA Molecules 1104

35.6 Conclusions 1108

References 1110

36 Cyclodextrin-Based Polyrotaxanes 1113
Akira Harada and Hiroyasu Yamaguchi

36.1 Rotaxanes 1113

36.2 Polyrotaxanes 1113

36.3 Rotaxanes Containing CDs 1113

36.4 Polyrotaxanes Containing CDs 1114

36.5 Formation of Gel by Mixing Host Polymers and Guest Polymers 1126

36.6 Tubular Polymers 1126

References 1126

37 Dendronized Polymers: An Approach to Single Molecular Objects 1131
Anzar Khan, Baozhong Zhang, and A. Dieter Schlüter

37.1 Introduction 1131

37.2 Synthesis 1133

37.3 Quantification of Thickness 1150

37.4 Responsivity of Dendronized Polymers 1150

37.5 Manipulation on Surfaces and Building Objects 1154

37.6 Conclusions 1156

Acknowledgments 1157

List of Symbols and Abbreviations 1157

References 1158

Index 1161

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