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The series Advances in Polymer Science presents critical reviews of the present and future trends in polymer and biopolymer science. It covers all areas of research in polymer and biopolymer science including chemistry, physical chemistry, physics, material science. The thematic volumes are addressed to scientists, whether at universities or in industry, who wish to keep abreast of the important advances in the covered topics. Advances in Polymer Science enjoys a longstanding tradition and good reputation in its community. Each volume is dedicated to a current topic and each review critically surveys one aspect of that topic, to place it within the context of the volume. The volumes typically summarize the significant developments of the last 5 to 10 years and discuss them critically, presenting selected examples, explaining and illustrating the important principles and bringing together many important references of primary literature. On that basis, future research directions in the area can be discussed. Advances in Polymer Science volumes thus are important references for every polymer scientist, as well as for other scientists interested in polymer science as an introduction to a neighboring field or as a compilation of detailed information for the specialist. Review articles for the individual volumes are invited by the volume editors. Single contributions can be specially commissioned. Readership: Polymer scientists or scientists in related fields interested in polymer and biopolymer science, at universities or in industry, graduate students.



Metal-Catalyzed Multicomponent Reactions for the Synthesis of Polymers

Despite the chemical complexity of multicomponent reactions (MCRs), the dawn of MCRs was fairly early in the history of organic chemistry. After lagging behind successful utilization of MCRs in combinatorial chemistry, the integration of MCRs with polymer chemistry has very recently started, which offers new possibilities in polymer synthesis. In spite of a large number of MCRs available for organic transformation reactions, this chapter describes metal-catalyzed MCRs in the area of polymer chemistry.
Ryohei Kakuchi

Multicomponent Polymerization of Alkynes

Multicomponent reactions (MCRs) are a group of unique reactions with a number of advantages such as atom economy, high efficiency, and simple procedure. These convenient reactions, especially MCRs based on alkyne monomers, are widely studied and extensively reported. However, polymerization methods based on MCRs of alkynes have rarely been developed to benefit the preparation of macromolecules. In this paper, up-to-date progress in the development of multicomponent polymerizations (MCPs) based on alkyne monomers is summarized, including MCP of alkynes, aldehydes and amines; MCP of alkynes, azides and amines/alcohols; and multicomponent tandem polymerization of alkynes, carbonyl chloride and thiols. Efforts in monomer screening, polymerization condition optimization, and structural characterization of the resultant polymer have generated a series of functional polymer materials with fascinating properties such as aggregation-induced/enhanced emission, light refractivity, photopatternability, and magnetism.
Rongrong Hu, Ben Zhong Tang

Biginelli Multicomponent Reactions in Polymer Science

The Biginelli reaction, a three-component cyclocondensation reaction, is an important member of the multicomponent reaction (MCR) family. The Biginelli reaction is so efficient and shares many similar properties as the recent click reactions. In this chapter, we summarised the current applications of the Biginelli reaction in polymer chemistry including polymer coupling, post polymer modification, and new functional polymer synthesis. We expect this ‘old’ reaction (>120 years) can draw attention from polymer chemists and play new roles in the polymer science.
Lei Tao, Chongyu Zhu, Yen Wei, Yuan Zhao

Passerini and Ugi Multicomponent Reactions in Polymer Science

Multicomponent reactions (MCRs) include more than two starting materials and are characterized by highly atom-efficient and straightforward practical procedures. Some of the most important MCRs in organic chemistry are the isocyanide-based MCRs, namely the Passerini three-component and Ugi four-component reaction. These reactions are, for example, often applied in combinatorial and medicinal chemistry due to their easy access to diversity or for the creation of complex structural motifs in the total synthesis of natural products.
Only recently, they also gained great interest in macromolecular chemistry, since the variation of the single components displays an easy tool to adjust the properties of the polymers and facile introduction of functional groups is enabled. Hereby, tailor-made high-performance and smart materials can be obtained, which are currently highly requested for many applications. In order to attain this objective, several strategies are followed: the MCRs are used to synthesize structurally diverse monomers for subsequent polymerization, or by the use of bifunctional components, these reactions are directly utilized as polymerization method. Moreover, the Passerini and Ugi reaction are applied in macromolecular engineering as conjugation method of two kinds of polymers, or as tool for grafting reactions as well as in the creation of defined primary structures. Finally, these valuable reactions are also used in the convergent and divergent synthesis of dendritic architectures.
Ansgar Sehlinger, Michael A. R. Meier

Sequential Thiol-Epoxy and Esterification Reactions: A Facile Route to Bifunctional Homopolymer Sequences

In this chapter, a post-polymerization double-modification strategy involving sequential thiol-epoxy and esterification reactions is discussed for the preparation of bifunctionalized homopolymer sequences. For this, initially, the synthesis and stability of poly(glycidyl methacrylate), the primary reactive scaffold, are considered. Double modification of the glycidyl units through consecutive thiol-epoxy and esterification reactions is then examined along with its potential to give rise to functionalized molecular bottlebrushes. Finally, application of this strategy for the preparation of amphipathic homopolymer sequences and their application in the arena of siRNA delivery are discussed.
Mihaiela C. Stuparu, Anzar Khan

One-Pot Double Modification of Polymers Based on Thiolactone Chemistry

One-pot multistep reactions based on thiolactone chemistry have emerged as a powerful tool for modifying thiolactone-containing polymers in one-pot and in an elegant manner. In general, thiolactones can be opened by a wide variety of functional amines and the released thiol can react with thiol ‘scavengers’ of choice. This overview highlights the most important features of this approach, illustrated by the versatile and site-specific double post-polymerization modification of various reactive systems.
Pieter Espeel, Filip E. Du Prez

Sequential Reactions for Post-polymerization Modifications

In this chapter, selected examples of sequential post-polymerization modifications are highlighted. Initially, we focus on side chain and chain end modifications in solution and at surface bounded polymers. Afterwards, the usage of this modifications as powerful tools in the synthesis of polymer structures such as graft and star polymers are discussed.
Fenja Moldenhauer, Patrick Theato

Sequential Post-modifications of Polybutadiene for Industrial Applications

Polybutadiene is a versatile starting material for polymer-analogous reactions because of the high content of easily accessed double bonds. It is a large scale polymeric product with relatively low costs. Polybutadiene may be tuned in its properties by consecutive chemical functionalizations to expand its range of applications. The polarity decreases content double bond hydrogenation and may be increased by the addition of heteroatoms to the olefinic entities. The functionalized of double bonds (e.g. to epoxides, aldehydes, carboxylates, hydroxyls or amines) opens the option of subsequent reactions in particular with nucleophilic reagents. This article focuses on post-modifications of polybutadiene homo-polymers by such sequential reactions and shows their relevance to applications.
Jan-Philipp Dilcher, Hannes Jürgens, Gerrit A. Luinstra


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