Synthesis of Polymers: New Structures and Methods(Materials Science and Technology: A Comprehensive Treatment)

Polymers are huge macromolecules composed of repeating structural units. While polymer in popular usage suggests plastic, the term actually refers to a large class of natural and synthetic materials. Due to the extraordinary range of properties accessible, polymers have come to play an essential and ubiquitous role in everyday life - from plastics and elastomers on the one hand to natural biopolymers such as DNA and proteins on the other hand. The study of polymer science begins with understanding the methods in which these materials are synthesized. Polymer synthesis is a complex procedure and can take place in a variety of ways. This book brings together the "Who is who" of polymer science to give the readers an overview of the large field of polymer synthesis. It is a one-stop reference and a must-have for all Chemists, Polymer Chemists, Chemists in Industry, and Materials Scientists.

Table of Contents:
LIST OF CONTRIBUTORS CONTENT OF VOLUME 1 FOREWORD References POLYMER SYNTHESIS: AN INDUSTRIAL PERSPECTIVE About this Chapter Why? Thesis: There Are No Limits to the Fantasy of a Synthetic Polymer Chemist Antithesis: We May Be Able to Synthesize Millions of New Polymers - But Why Should We Do So? Synthesis Conclusions FROM HETEROGENEOUS ZIEGLER?NATTA TO HOMOGENEOUS SINGLE-CENTER GROUP 4 ORGANOMETALLIC CATALYSTS: A PRIMER ON THE COORDINATION POLYMERIZATION OF OLEFINS Introduction Chapter Prospectus Fundamentals of Coordination Polymerization Homogeneous Single-Center Coordination Polymerization Conclusions COBALT-MEDIATED RADICAL POLYMERIZATION Introduction Mechanistic Considerations Key Parameters of CMRP Macromolecular Engineering Cobalt-Mediated Radical Coupling (CMRC) Summary and Outlook ANIONIC POLYMERIZATION: RECENT ADVANCES Background Living Anionic Polymerization of Various Monomers (Meth)acrylate Derivatives Acrylamide Derivatives Acrylamide Derivatives Cyclic Monomers Other Monomers Reaction of Living Anionic Polymers with Electrophiles: Synthesis of Chain-Functionalized Polymers Synthesis of Architectural Polymers via Living Anionic Polymerization Anionic Polymerization: Practical Aspects Concluding Remarks ALKYNE METATHESIS POLYMERIZATION (ADIMET) AND MACROCYCLIZATION (ADIMAC) Introduction Catalyst Development Poly(Phenylene Ethynylene)s via ADIMET ADIMAC-Acyclic Diyne Metathesis Macrocyclization Conclusions THE SYNTHESIS OF CONJUGATED POLYTHIOPHENES BY KUMADA CROSS-COUPLING Introduction to Polythiophene Kumada Cross-Coupling Polythiophenes by Kumada Cross-Coupling Copolymers Summary and Outlook "ABSOLUTE" ASYMMETRIC POLYMERIZATION WITHIN CRYSTALLINE ARCHITECTURES: RELEVANCE TO THE ORIGIN OF HOMOCHIRALITY Introduction "Through-Space" Asymmetric Polymerization in Inclusion Complexes and Liquid Crystals Isotactic Oligomers Generated within Monolayers at the Air?Water Interface "Absolute" Asymmetric Polymerization in 3-D Crystals Generation of Isotactic Oligopeptides via Polymerization in Racemic Crystals Isotactic Oligopeptides from the Polymerization of Racemic ValNCA or LeuNCA in Aqueous Solution Racemic ?-Sheets in the Polymerization of a-Amino-Acids in Aqueous Solutions: Homochiral Oligopeptides and Copeptides via the "Ehler-Orgel" Reaction Isotactic Oligopeptides from Racemic Thioesters of DL-Leu and DL-Val Conclusions SYNTHESIS OF ABIOTIC FOLDAMERS Introduction Phenylene Ethynylene Foldamers Helical Aromatic Amides Helical Aromatic Ureas Helical Aromatic Hydrazides Heterocyclic Foldamers Conclusions CYLINDRICAL POLYMER BRUSHES Introduction Synthesis of CPBs Properties of CPBs CPBs as a Template for 1-D Inorganic/Hybrid Nanostructures Closing Remarks BLOCK COPOLYMERS BY MULTI-MODE POLYMERIZATIONS Introduction Coupling Methods Transformation Reactions Dual Polymerizations Conclusions ADVANCES IN THE SYNTHESIS OF CYCLIC POLYMERS Introduction Bimolecular Approach Unimolecular Approach Ring-Expansion Approach Conclusions CYCLODEHYDROGENATION IN THE SYNTHESIS OF GRAPHENE-TYPE MOLECULES Introduction Lewis Acid-Catalyzed Oxidative Cyclodehydrogenation (Scholl Reaction) Base-Induced Cyclodehydrogenation Oxidative Photocyclization (Mallory Reaction) Surface-Assisted Cyclodehydrogenation Conclusions POLYMERIZATIONS IN MICRO-REACTORS Introduction Polymerization Reactions with Excess Heat Production Formation of Uniform Particles Scaling-Up Conclusions MINIEMULSION POLYMERIZATION Introduction Radical Polymerization Controlled Radical Polymerizations Radiation-Induced Polymerization Metal-Catalyzed Polymerizations Ionic Polymerizations Polyaddition Polycondensation Enzymatic Polymerization Oxidative Polymerization New Synthetic Approaches in Miniemulsion Conclusions NEW CONJUGATED POLYMERS AND SYNTHETIC METHODS Introduction New Polymers Prepared via Chain-Growth Methods Mechanism Remaining Limitations Conclusions and Outlook POLYCATENANES Introduction Main-Chain Polycatenanes Side-Chain Polycatenanes Polymeric Catenanes Catenane Structures in Polymer Networks Conclusions and Perspective MULTICYCLIC POLYMERS Introduction Ring Polymers with Branches ("Tadpoles") Dicyclic Polymers Tricyclic and Tetracyclic Polymers Oligocyclic Polymers Conclusions and Perspectives CONTENT OF VOLUME 2 RING-OPENING METATHESIS POLYMERIZATION Introduction to Ring-Opening Metathesis Polymerization (ROMP) Well-Defined Transition Metal-Based Initiators for ROMP Latent Initiators for ROMP "Living" ROMP Summary and Outlook RECENT ADVANCES IN ADMET POLYCONDENSATION CHEMISTRY Introduction Functionalized Polyethylenes Functional Polymers and Materials via ADMET Exotic Polymer Structures Summary and Outlook MACROMOLECULAR ENGINEERING VIA RAFT CHEMISTRY: FROM SEQUENTIAL TO MODULAR DESIGN Introduction Sequential Design Modular Design Conclusions SUZUKI POLYCONDENSATION Introduction General Remarks How to Perform SPC, and Aspects of Characterization Recent Progress in Broadening the Scope of SPC Selected Examples of Polyphenylenes and Related Polymers by SPC Conclusions and Outlook ENZYMATIC POLYMERIZATION Introduction Enzymatic Synthesis of Phenolic Polymers Enzymatic Synthesis of Polyesters Concluding Remarks HYPERBRANCHED POLYMERS: SYNTHESIS AND CHARACTERIZATION ASPECTS Introduction Synthetic Methodologies Characterization Aspects Separation Techniques for hb Polymers Size Determination and Scaling Parameters of hb Polymers Conclusions EMULSION POLYMERIZATION Introduction Molecular Description of Emulsion Polymerization Radical Polymerization Kinetics in Emulsion Polymerization Conclusion CARBOCATIONIC POLYMERIZATION Introduction Mechanistic and Kinetic Details of Living Cationic Polymerization Living Cationic Polymerization Functional Polymers by Living Cationic Polymerization Telechelic Polymers Macromonomers Linear Diblock Copolymers Linear Triblock Copolymers Block Copolymers with Nonlinear Architecture Branched and Hyperbranched Polymers Surface Initiated Polymerization - Polymer Brushes Conclusions FROM STAR-LIKE TO DENDRIMER-LIKE POLYMERS Introduction Essential Features and Properties of Stars and Dendrimer-Like Polymers General Methods for the Synthesis of Star Polymers General Methods for the Synthesis of Dendrimer-Like Polymers Conclusions TWO-DIMENSIONAL POLYMERS Introduction Why 2-D Polymers? What Is Not Considered a 2-D Polymer? General Considerations on Rational 2-D Polymer Synthesis Approaches to 2-D Polymers and Related Structures Conclusions and Outlook POLY( PARA-PHENYLENE VINYLENE)S Introduction Step-Growth Syntheses of PPVs Chain-Growth Syntheses of PPVs Conclusions and Outlook "CLICk" CHEMISTRY IN POLYMER SCIENCE: CUAAC AND THIOL-ENE COUPLING FOR THE SYNTHESIS AND FUNCTIONALIZATION OF MACROMOLECULES Introduction and Perspective Polymers from "Click" Chemistry Summary and Conclusions CARBENES IN POLYMER SYNTHESIS Introduction to Carbenes Carbenes as Structural Components of Macromolecules Carbene-Based Polymerization Catalysts Conclusions POLYMERIZATION IN CONFINED GEOMETRIES Introduction Polymer Synthesis in Organic Hosts Polymerization in Inorganic Hosts Polymer Synthesis in Organic - Inorganic Hybrid Hosts Summary and Conclusions ACCELERATED APPROACHES TO DENDRIMERS Introduction Classification and Synthesis Accelerated Synthesis of Dendrimers Summary and Conclusions SUPRAMOLECULAR POLYMERS Introduction Supramolecular Chemistry Supramolecular Polymerization Mechanisms Examples of Supramolecular Polymers Supramolecular Polymeric Materials Future Perspectives NUCLEIC ACID POLYMERS AND DNA SYNTHETIC POLYMER HYBRID MATERIALS GENERATED BY MOLECULAR BIOLOGY TECHNIQUES Introduction DNA Hydrogels Mediated by the Action of DNA Ligases DNA Block Copolymers and DNA Networks Generated by the Polymerase Chain Reaction Generating DNA - Synthetic Polymer Hybrids with DNA Polymerases Plasmids and Catenated Nucleic Acid Architectures from Circular DNA Molecules Conclusions CYCLODEXTRIN-BASED PLYROTAXANES Rotaxanes Polyrotaxanes Rotaxanes Containing CDs Polyrotaxanes Containing CDs Formation of Gel by Mixing Host Polymers and Guest Polymers Tubular Polymers DENDRONIZED POLYMERS: AN APPROACH TO SINGLE MOLECULAR OBJECTS Introduction Synthesis Quantification of Thickness Responsivity of Dendronized Polymers Manipulation on Surfaces and Building Objects Conclusions INDEX

About the Author :
A. Dieter Schluter is since 2004 Professor for polymer chemistry at the Materials Department of the ETH Zurich. 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 fur 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. Frechet 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. Mullen 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. Schluter 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.