Synthesis of Polymers -- Contents -- List of Contributors -- 1 Foreword -- References -- 2 Polymer Synthesis: An Industrial Perspective -- 2.1 About this Chapter -- 2.2 Why? -- 2.3 Thesis: There Are No Limits to the Fantasy of a Synthetic Polymer Chemist -- 2.4 Antithesis: We May Be Able to Synthesize Millions of New Polymers-But Why Should We Do So? -- 2.5 Synthesis -- 2.5.1 Polymer Chemistry in Two Dimensions: Coatings -- 2.5.2 Polymer Chemistry Going Broad: Effects of Molar Mass Distribution -- 2.5.3 Polymer Chemistry Meets The Life Sciences: Polymeric Drug-Delivery Systems -- 2.6 Conclusions -- Acknowledgments -- 3 From Heterogeneous Ziegler-Natta to Homogeneous Single-Center Group 4 Organometallic Catalysts: A Primer on the Coordination Polymerization of Olefins -- 3.1 Introduction -- 3.2 Chapter Prospectus -- 3.3 Fundamentals of Coordination Polymerization -- 3.3.1 Ziegler-Natta Catalysts -- 3.3.1.1 First-Generation ZN Catalysts -- 3.3.1.2 Second-Generation ZN Catalysts -- 3.3.1.3 Third-Generation ZN Catalysts -- 3.3.1.4 Fourth-Generation ZN Catalysts -- 3.3.1.5 Fifth-Generation ZN Catalysts -- 3.3.2 Cossee-Arlman Mechanism -- 3.3.3 Stereocontrol -- 3.3.4 Regiocontrol -- 3.3.5 Chain Termination -- 3.3.6 Molecular Weight Distributions and Branching -- 3.4 Homogeneous Single-Center Coordination Polymerization -- 3.4.1 Molecular Catalysts -- 3.4.2 Metallocenes -- 3.4.3 Stereocontrol -- 3.4.4 Stereochemical Microstructure Analysis -- 3.4.5 Cocatalysts -- 3.5 Conclusions -- Acknowledgments -- References -- 4 Cobalt-Mediated Radical Polymerization -- 4.1 Introduction -- 4.2 Mechanistic Considerations -- 4.3 Key Parameters of CMRP -- 4.3.1 The Cobalt Complex Structure -- 4.3.2 Polymerization Conditions -- 4.4 Macromolecular Engineering -- 4.5 Cobalt-Mediated Radical Coupling (CMRC) -- 4.6 Summary and Outlook -- Acknowledgments -- References.

5 Anionic Polymerization: Recent Advances -- 5.1 Background -- 5.2 Living Anionic Polymerization of Various Monomers -- 5.2.1 Styrene Derivatives -- 5.2.2 1,3-Diene Monomers -- 5.2.3 2- and 4-Vinylpyridines -- 5.3 (Meth)acrylate Derivatives -- 5.4 Acrylamide Derivatives -- 5.5 Cyclic Monomers -- 5.6 Other Monomers -- 5.7 Reaction of Living Anionic Polymers with Electrophiles: Synthesis of Chain-Functionalized Polymers -- 5.8 Synthesis of Architectural Polymers via Living Anionic Polymerization -- 5.8.1 Block Copolymers -- 5.8.2 Graft Copolymers -- 5.8.3 Star-Branched Polymers -- 5.8.4 Complex Architectural Polymers -- 5.9 Anionic Polymerization: Practical Aspects -- 5.10 Concluding Remarks -- References -- 6 Alkyne Metathesis Polymerization (ADIMET) and Macrocyclization (ADIMAC) -- 6.1 Introduction -- 6.2 Catalyst Development -- 6.3 Poly(Phenylene Ethynylene)s via ADIMET -- 6.4 ADIMAC-Acyclic Diyne Metathesis Macrocyclization -- 6.5 Conclusions -- References -- 7 The Synthesis of Conjugated Polythiophenes by Kumada Cross-Coupling -- 7.1 Introduction to Polythiophene -- 7.2 Kumada Cross-Coupling -- 7.3 Polythiophenes by Kumada Cross-Coupling -- 7.3.1 Initiation and Catalyst Transfer Propagation -- 7.3.2 Summary of Mechanistic Studies -- 7.3.3 Influence of the Catalyst on Regioregularity -- 7.3.4 Thiophene-Based Monomers -- 7.3.5 Non-Thiophene Monomers -- 7.3.6 End Group Modification -- 7.4 Copolymers -- 7.4.1 Random and Alternating Copolymers -- 7.4.2 Block Copolymers -- 7.5 Summary and Outlook -- References -- 8 ''Absolute'' Asymmetric Polymerization within Crystalline Architectures: Relevance to the Origin of Homochirality -- 8.1 Introduction -- 8.2 ''Through-Space'' Asymmetric Polymerization in Inclusion Complexes and Liquid Crystals -- 8.3 Isotactic Oligomers Generated within Monolayers at the Air-Water Interface.

8.4 ''Absolute'' Asymmetric Polymerization in 3-D Crystals -- 8.4.1 The Planning and Materialization of an ''Absolute'' Asymmetric Synthesis of Polymers -- 8.4.2 Attempted Amplification of Homochirality -- 8.5 Generation of Isotactic Oligopeptides via Polymerization in Racemic Crystals -- 8.5.1 (RS)-PheNCA -- 8.5.2 (RS)-ValNCA and (RS)-LeuNCA -- 8.6 Isotactic Oligopeptides from the Polymerization of Racemic ValNCA or LeuNCA in Aqueous Solution -- 8.7 Racemic ß-Sheets in the Polymerization of a-Amino-Acids in Aqueous Solutions: Homochiral Oligopeptides and Copeptides via the ''Ehler-Orgel'' Reaction -- 8.8 Isotactic Oligopeptides from Racemic Thioesters of DL-Leu and DL-Val -- 8.9 Conclusions -- References -- 9 Synthesis of Abiotic Foldamers -- 9.1 Introduction -- 9.2 Phenylene Ethynylene Foldamers -- 9.2.1 Backbone Folding: Design Principle -- 9.2.2 General Synthesis -- 9.2.3 Representative Examples -- 9.2.3.1 Oligo(meta-Phenylene Ethynylene)s (OmPEs) -- 9.2.4 Oligo(ortho-Phenylene Ethynylene)s (OoPEs) -- 9.3 Helical Aromatic Amides -- 9.3.1 Backbone Folding: Design Principle -- 9.3.2 General Synthesis -- 9.3.3 Representative Examples -- 9.3.3.1 Oligoaryl-Dicarboxamides -- 9.3.3.2 Oligoquinoline-Dicarboxamides -- 9.3.3.3 Oligoanthranilamides -- 9.3.3.4 Oligopyridine-Dicarboxamides -- 9.4 Helical Aromatic Ureas -- 9.4.1 Backbone Folding: Design Principle -- 9.4.2 General Synthesis -- 9.4.3 Representative Examples -- 9.4.3.1 Oligoheterocyclic Ureas -- 9.4.3.2 Oligoaryl Ureas -- 9.4.3.3 Oligobenzoyl Ureas -- 9.5 Helical Aromatic Hydrazides -- 9.5.1 Backbone Folding: Design Principle -- 9.5.2 Synthesis -- 9.6 Heterocyclic Foldamers -- 9.6.1 Backbone Folding: Design Principle -- 9.6.2 Representative Examples -- 9.6.2.1 Oligopyridine-Pyrimidines -- 9.6.2.2 Oligopyridine-Pyridazines -- 9.6.2.3 Oligonaphthyridine-Pyrimidines.

9.6.2.4 1,4-Disubstituted-1,2,3-Triazoles -- 9.6.2.5 Oligoindoles -- 9.7 Conclusions -- Abbreviations -- References -- 10 Cylindrical Polymer Brushes -- 10.1 Introduction -- 10.2 Synthesis of CPBs -- 10.2.1 Grafting-Through Strategy -- 10.2.1.1 Homopolymerization of Macromonomers -- 10.2.1.2 Copolymerization by Grafting-Through -- 10.2.2 Grafting-Onto Strategy -- 10.2.2.1 Side-Chain Attachment by Nucleophilic Substitution -- 10.2.2.2 Side-Chain Attachment by ''Click'' Chemistry -- 10.2.3 Grafting-From Strategy -- 10.2.3.1 Polyinitiator Backbone -- 10.2.4 Side-Chain Composition -- 10.2.4.1 Homopolymer Side Chains -- 10.2.4.2 Core-Shell Diblock Copolymer Side Chains -- 10.2.4.3 Other Copolymer Side Chains -- 10.2.5 Combined Grafting Approach -- 10.2.5.1 Grafting-Onto + Grafting-From -- 10.2.5.2 Grafting-Through + Grafting-From -- 10.2.6 Block Copolymer Self-Assembly -- 10.2.6.1 Selective Crosslinking in Bulk -- 10.2.6.2 Core Crystallization in Solution -- 10.2.6.3 Comparison with Molecular Brushes -- 10.3 Properties of CPBs -- 10.3.1 Solution Properties -- 10.3.2 Properties in the Bulk -- 10.3.3 CPBs in Thin Films on Different Substrates -- 10.4 CPBs as a Template for 1-D Inorganic/Hybrid Nanostructures -- 10.4.1 Core-Shell CPBs as a Template -- 10.4.2 Polymeric Cylinders from Self-Assembly as a Template -- 10.5 Closing Remarks -- References -- 11 Block Copolymers by Multi-Mode Polymerizations -- 11.1 Introduction -- 11.2 Coupling Methods -- 11.3 Transformation Reactions -- 11.3.1 Transformations Involving Anionic and Controlled Radical Polymerization -- 11.3.2 Transformations Involving Cationic and Controlled Radical Polymerization -- 11.3.3 Transformations Involving Anionic and Cationic Polymerizations -- 11.3.4 Transformations Involving Metathesis Polymerization -- 11.3.5 Transformations Involving Ziegler-Natta Polymerization.

11.3.6 Transformations Involving the Same Polymerization Mechanism -- 11.4 Dual Polymerizations -- 11.5 Conclusions -- List of Symbols and Abbreviations -- References -- 12 Advances in the Synthesis of Cyclic Polymers -- 12.1 Introduction -- 12.2 Bimolecular Approach -- 12.3 Unimolecular Approach -- 12.3.1 Homodifunctional Approach -- 12.3.2 Heterodifunctional Approach -- 12.4 Ring-Expansion Approach -- 12.5 Conclusions -- References -- 13 Cyclodehydrogenation in the Synthesis of Graphene-Type Molecules -- 13.1 Introduction -- 13.2 Lewis Acid-Catalyzed Oxidative Cyclodehydrogenation (Scholl Reaction) -- 13.2.1 Hexa-peri-Hexabenzocoronenes (HBCs) and Related Systems -- 13.2.2 Expanded PAHs: Nanographenes and Graphene Nanoribbons -- 13.3 Base-Induced Cyclodehydrogenation -- 13.4 Oxidative Photocyclization (Mallory Reaction) -- 13.5 Surface-Assisted Cyclodehydrogenation -- 13.6 Conclusions -- References -- 14 Polymerizations in Micro-Reactors -- 14.1 Introduction -- 14.1.1 The Micro-Reactor -- 14.1.2 Droplet Formation -- 14.2 Polymerization Reactions with Excess Heat Production -- 14.2.1 Step Growth Polymerization -- 14.2.2 Chain Growth Polymerization -- 14.2.3 Anionic Polymerization -- 14.2.4 Cationic Polymerization -- 14.2.5 Radical Polymerization -- 14.2.5.1 Solution Free Radical Polymerization -- 14.2.5.2 Controlled Radical Polymerization -- 14.3 Formation of Uniform Particles -- 14.3.1 Particle Formation by Precipitation/Dispersion Polymerization -- 14.3.2 Continuous Production of Monodisperse Polymer Particles -- 14.4 Scaling-Up -- 14.5 Conclusions -- References -- 15 Miniemulsion Polymerization -- 15.1 Introduction -- 15.2 Radical Polymerization -- 15.3 Controlled Radical Polymerizations -- 15.4 Radiation-Induced Polymerization -- 15.5 Metal-Catalyzed Polymerizations -- 15.6 Ionic Polymerizations -- 15.7 Polyaddition -- 15.8 Polycondensation.

15.9 Enzymatic Polymerization.