In modern polymer science a variety of polymerization methods for the direct synthesis of polymers bearing functional groups are known. However, there is still a large number of functional groups that may either completely prevent polymerization or lead to side reactions. Post-polymerization modification, also known as polymer-analogous modification, is an alternative approach to overcome these limitations. It is based on the polymerization of monomers with functional groups that are inert towards the polymerization conditions but allow a quantitative conversion in a subsequent reaction step yielding a broad range of other functional groups. Thus, diverse libraries of functional polymers with identical average degrees of polymerization but variable side chain functionality may easily be generated. 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 with examples ranging from modification of biomimetic and biological polymers to modification of surfaces. With its guidelines this is an indispensable and interdisciplinary reference for scientists working in both academic and industrial polymer research.

Post-polymerization modification of polymers is an important tool for accessing macromolecular materials with desired functional groups and tailored properties. Such strategy may become the only route to a target polymer when the availability or reactivity of the corresponding monomer is not suited for direct polymerization. Most post-polymerization modification processes are based on transforming functional groups that are pre-installed in the side chains or chain-ends of a polymer. Despite the excellent efficiency and versatility, they are limited to certain backbone structures and often require additional synthetic effort for the synthesis of the corresponding pre-functionalized monomers. More specifically, they are useful only when the pre-functionalized monomers can be readily prepared and incorporated to a polymer by direct polymerization. In contrast, direct functionalization of C-H bonds along the polymer backbone offers a markedly different strategy for the synthesis of functional polymers. Despite the inert nature, the ubiquity of the C-H bonds and their tunable reactivity make them ideal targets for selective chemical modification. In this dissertation, it is first demonstrated that poly(vinyl ester)s and poly(vinyl ether-co-vinyl ester) can be readily prepared via a ruthenium catalyzed C–H oxyfunctionalization of the corresponding poly(vinyl ether)s under mild conditions. The method can be further applied for the synthesis of high molecular weight poly(propenyl ester)s which cannot be obtained using other methods. In addition the method allows poly(isopropenyl ester) to be synthesized without the use of extremely high pressures. Using a similar strategy poly(ethylene glycol-co-glycolic acid) can be prepared by the ruthenium-catalyzed oxidation of poly(ethylene glycol) (PEG). A new process has been developed so that the transformation will cause little chain degradation. The presence of the hydrolytically labile ester groups in the PEG backbone renders the copolymer biodegradable, which may allow the PEG of higher molecular weight to be used in biomedical applications without the concerns of bioaccumulation of PEG into various organs. Lastly, it is demonstrated that azido-functionalized, isotactic polypropylene can be prepared via the direct C–H azidation of a commercially available polymer using a stable azidoiodinane. The azidated PP can further undergo copper-catalyzed azide-alkyne cycloaddition with alkyne terminated polymer to obtain PP-based graft copolymers. It is expected that the ability to incorporate versatile functional groups, such as azides, into common polyolefin feedstocks should expand their applications and potentially enable the realization of new classes of materials.

Direct polymerization of isocyanate-functional monomers has been achieved with controlled radical polymerizations (CRP) for precisely engineered modification platforms with highly reactive side chains. However, despite the success of these strategies, the inherent reactivity of isocyanates still leads to adverse side reactions, such as hydrolysis, that are difficult to suppress. Phenol, lactam, and oxime-based blocking agents have been used to limit the reactivity of isocyanates in applications such as multicomponent urethane coating systems. The reactivity of these blocked isocyanates can be restored by thermal deprotection of the blocking agent to achieve the desired reactions. In this work, we use blocked isocyanate-functional monomers for surface-initiated polymerization. The isocyanate functional group allows facile modification of the side chains by thiolisocyanate "click" reactions, while the blocking agent reduces detrimental side reactions like hydrolysis. We investigate thermally labile blocking agents and report the synthesis and characterization of the blocked isocyanate-functional polymers, followed by deprotection and modification of the isocyanates by reaction with thiols. --Page iv.

The research in this thesis focuses predominately on the preparation and characterization of polymers and block copolymers containing ionizable or charged moieties. In the first part of this thesis, the synthesis and polymerization of various monomers is described, which are converted into polyelectrolytes and polyampholytes with a high charge density later on. Such functional materials are highly versatile, finding use as surfactants, in heterogeneous catalysis, or in biomedical applications. In the second part of this thesis, polyether-based block copolymers are prepared by anionic ring-opening polymerization for use in gene and drug delivery.

This book describes strategies and mechanism of reversible deactivation radical polymerization (RDRP) to synthesize functional polymers. Several approaches such as atom transfer radical polymerization and the combination of click chemistry and RDRP are summarized. Contributors from interdisciplinary fields highlight applications in nanotechnology, self-healing materials, oil and water resistant coatings and controlled drug delivery systems.

This book gathers the various aspects of the porous polymer field into one volume. It not only presents a fundamental description of the field, but also describes the state of the art for such materials and provides a glimpse into the future. Emphasizing a different aspect of the ongoing research and development in porous polymers, the book is divided into three sections: Synthesis, Characterization, and Applications. The first part of each chapter presents the basic scientific and engineering principles underlying the topic, while the second part presents the state of the art results based on those principles. In this fashion, the book connects and integrates topics from seemingly disparate fields, each of which embodies different aspects inherent in the diverse field of porous polymeric materials.

Understanding the reactivity of monomers is crucial in creating copolymers and determining the outcome of copolymerization. Covering the fundamental aspects of polymerization, Synthesis and Applications of Copolymers explores the reactivity of monomers and reaction conditions that ensure that the newly formed polymeric materials exhibit desired properties. Referencing a wide-range of disciplines, the book provides researchers, students, and scientists with the preparation of a diverse variety of copolymers and their recent developments, with a particular focus on copolymerization, crystallization, and techniques like nanoimprinting and micropatterning.