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Polymers form the basis of our daily lives. Natural polymers such as starch and cotton provide the source of food and clothes while synthetic polymers such as polyurethanes, polycarbonates, and polyamides have revolutionized almost every aspect of modern life with extensive applications in clothes, packing materials, medical apparatus and even aerospace crafts. The development of polymers depends largely on the advancement of synthetic methodologies. Traditional methodologies such as anionic and radical polymerizations play significant roles in preparing various functional polymers. However, the increasing demand for polymers with new structures and functions has inspired the development of new polymerization techniques. Many new polymerizations including the metal-catalyzed coupling polymerization, controlled/living radical polymerization etc. have been well developed to provide efficient tools for the synthesis of various linear and topological polymers with conjugated and non-conjugated structures. In addition to developing new polymerizations, the art of monomer design and post-polymerization are also important in endowing polymers with specific functionality. In this case, multicomponent polymerization and click polymerization have attracted great attention in the past decades. Due to the demand for fundamental research and new polymers for advanced technology, research interest in polymer synthesis continues to grow. This book thus aims to introduce some of the latest developments and breakthroughs in synthetic polymer chemistry.

This book consists of 10 chapters contributed by leading experts in the field of synthetic polymer chemistry covering the areas of click polymerization, olefin co(polymerization), fabrication of supramolecular polymers, carbon dioxide copolymers etc. It mainly focuses on the novel strategies or methodologies to prepare polymers with diverse shapes and functions, and topics including monomer design, catalyst design, and new polymerization strategies will be discussed.

In Chapter 1, Dong and Wang et al. introduced new polysulfonate and polysulfate polymers via “sulfur(vi) fluoride exchange” (SuFEx) click chemistry, especially focusing on the evolution of the catalysts involved. Aside from the discovery of new polymers, SuFEx click chemistry as a powerful tool in polymer modification was also discussed. In Chapter 2, Zhang and coworkers overviewed the general mechanisms of major reactions in thiol chemistry with a focus on their significance and potential applications. The release of thiol groups, the efficient reactions of the thiol group, and the contribution of thiol chemistry in precise polymer synthesis were also described. In Chapter 3, Zhang and Hadjichristidis presented the strategies to synthesize well-defined polyethylene (PE) stars from the mature anionic polymerization of butadiene and hydrogenation and the recently discovered polyhomologation (C1 polymerization) of dimethylsulfoxonium methylylide. The ring-opening metathesis polymerization of monocyclic alkenes followed by hydrogenation, and the Pd-diimine catalyzed “ethylene” polymerization towards PE stars were also briefly reviewed. In Chapter 4, Xu and Zhang overviewed the fabrication of supramolecular polymers and introduced the driving forces for supramolecular polymerization, summarized the topological structures of supramolecular polymers, and highlighted the methods and strategies for the fabrication of supramolecular polymers in a controllable manner. In Chapter 5, Tang and co-workers introduced the olefins (co)polymerizations enabled by catalyst design based on the side arm strategy, from which the activity of the resulting catalyst complexes increased obviously and the newly-designed SaBOX played a key role in a highly syndiospecific (>90% rr) and controlled atom transfer radical polymerization (ATRP) of methyl methacrylate, allyl methacrylate and vinyl methacrylate under mild polymerization conditions. In Chapter 6, Lu et al. overviewed the most recent developments of desymmetrization copolymerization of meso-epoxides with various achiral reaction partners. In particular, they highlighted the role of multichiral induction, intramolecular bimetallic synergistic effects in determining the reactivity and enantioselectivity. In Chapter 7, Wang and co-workers gave an overview on the advanced catalysis of CO2/epoxide copolymerization and the unique material properties of the resulting copolymers. Emphasis was placed on the hope of CO2 based copolymers for the biodegradable plastics industry and low-molecular-weight CO2-polyols with non-alternative structures as new building blocks in the polyurethane industry. In Chapter 8, Tao and co-workers proposed the use of bases for the ring-opening polymerization of cyclic lysine monomer to poly(ε-lysine) with high molecular weight. And this improvement has created new chances for industrial use. In Chapter 9, Tang and co-workers summarized the progress of synthetic fused (hetero)cyclic polymers by alkyne-based polymerizations; the properties and functionalities of the produced fused (hetero)cyclic polymers were also discussed. In Chapter 10, Zhang and co-workers highlighted the recent advances in organocatalytic copolymerizations of carbon dioxide and carbonyl sulfide (COS), which were two typical one-carbon (C1) building blocks. The synthesis of various types of CO2(COS)-based copolymers, the organocatalytic mechanism and the properties of C1-based copolymers were also introduced. This book will provide an excellent reference for polymer chemists, organic chemists, catalysis and materials scientists at graduate level and above.

With the comprehensive reviews on the recent advancements in polymer synthesis from the leading experts around the world, we hope this book will provide a useful source of information and a practical guide for scientists, engineers and students that are interested in this field.

Zheng Zhao

Rong Hu

Anjun Qin

Ben Zhong Tang

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