聚合物支载的有机催化剂Ⅰ.非手性有机催化剂

对二十余年来聚合物支载的有机催化剂的合成、性能及其在催化反应中的应用,包括负载催化剂的回收和重复使用等进行了综述.用于支载体的聚合物包括交联聚合物、线型聚合物及树形聚合物;支载的有机催化剂包括手性及非手性催化剂两类.本文作为第一部分将介绍聚合物支载的非手性有机催化剂,包括相转移催化剂、氧化催化剂、酸以及碱催化剂.     

Recent advances of CuAAC click reaction in building cyclic polymer

Cyclic polymers have attracted more and more attentions in recent years because of their unique topological structures and characteristic properties in both solution and bulk state. There are relatively few reports on cyclic polymers, partly because of the more demanding synthetic procedures. In recent years, “click” reaction, especially Cu(I)-catalyzed azide-alkyne cycloaddition (CuAAC), has been widely utilized in the synthesis of cyclic polymer materials because of its high efficiency and low susceptibility to side reactions. In this review, we will focus on three aspects: (1) Constructions of monocyclic polymer using CuAAC “click” chemistry; (2) Formation of complex cyclic polymer topologies through CuAAC reactions; (3) Using CuAAC “click” reaction in the precise synthesis of molecularly defined macrocycles. We believe that the CuAAC click reaction is playing an important role in the design and synthesis of functional cyclic polymers.     

聚合物支载的有机催化剂Ⅱ.手性有机催化剂

对二十余年来聚合物支载的有机催化剂的合成、性能及其在催化反应中的应用,包括负载催化剂的回收和重复使用等进行了综述。用于支载体的聚合物包括交联聚合物、线型聚合物及树形聚合物;支载的有机催化剂包括手性及非手性催化剂两类。本文作为第二部分将介绍聚合物支载的手性有机催化剂,重点介绍近年来颇受重视的氨基酸及多肽类有机催化剂的研究及其应用进展。     

“点击”反应在制备环状聚合物中的应用

环状聚合物具有不同于线性高分子的独特性质,是一类具有应用前景的新型聚合物材料,但复杂的结构导致其合成过程复杂繁琐.＂点击＂化学由于其高效、可靠、高选择性的特点已成为拓扑高分子合成的新方法,活性自由基聚合（ATRP、RAFT和NMP）具有聚合物结构可控等特点,二者联用为环状聚合物的合成拓宽了思路.本文就近几年＂点击＂反应、＂点击＂反应与活性自由基聚合联用以及其他方法联用在环状聚合物中的应用进行综述.＂点击＂反应与这些方法的结合将在功能性环状聚合物的设计与合成中发挥积极的作用.     

Stepping Further from Coupling Tools: Development of Functional Polymers via the Biginelli Reaction

Multicomponent reactions (MCRs) have been used to prepare polymers with appealing functions. The Biginelli reaction, one of the oldest and most famous MCRs, has sparked new scientific discoveries in polymer chemistry since 2013. Recent years have seen the Biginelli reaction stepping further from simple coupling tools; for example, the functions of the Biginelli product 3,4-dihydropyrimidin-2(1H)-(thi)ones (DHPM(T)) have been gradually exploited to develop new functional polymers. In this mini-review, we mainly summarize the recent progress of using the Biginelli reaction to identify polymers for biomedical applications. These polymers have been documented as antioxidants, anticancer agents, and bio-imaging probes. Moreover, we also provide a brief introduction to some emerging applications of the Biginelli reaction in materials and polymer science. Finally, we present our perspectives for the further development of the Biginelli reaction in polymer chemistry.     

The synthesis of cyclic polymers by olefin metathesis: Achievements and challenges

Cyclic polymers have drawn considerable interest for their peculiar physical properties in comparison to linear polymers, despite their equivalent compositions. Synthetically, cyclic polymers can be accessed through either macrocyclic ring‐closure or by ring‐expansion polymerization, but the main challenge with either method is the production of highly pure cyclic polymer samples. This highlight describes advances in the area of cyclic polymer synthesis, with a particular focus on ring‐expansion metathesis polymerization. Methods for characterizing cyclic polymers and assessing their purity are also discussed in order to emphasize the need for additional robust and reliable methods for synthesizing and studying topologically complex macromolecules. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 228–242     

An overview of synthetic modification of nitrile group in polymers and applications

The physicochemical properties of polymers are mainly dependent on the nature of polymer backbone and/or pendant groups linked to the main chain. Therefore, synthetic modification of these functional groups via post functionalization is an important approach for obtaining novel polymeric systems with improved properties and targeted applications. In this context, the synthetic modifications of nitrile group in polymers into various useful functionalities have received considerable attention and several interesting applications of the resulting polymers have been identified. The majority of the studies are based on Polyacrylonitrile (PAN), and some isolated examples of nitrile functionalization in copolymers such as Poly (Styrene-co-Acrylonitrile) (SAN), Poly (Acrylonitrile-co-Butadiene-co-Styrene (ABS) and Nitrile Rubber (NBR) are available. These synthetic modifications are mainly accomplished by the reactions such as Nucleophilic addition, cycloaddition, reduction, and hydrolysis using various reagents. These studies describing the post-polymerization modifications of nitrile group in polymers reported during the last three decades are covered in this review.     

Applications of phosphine-functionalised polymers in organic synthesis

This tutorial review deals with recent advances in the use of phosphine-functionalised polymers in organic synthesis. In the first part of the review, some recent applications of polymer-supported palladium catalysts are reviewed, particularly recyclable catalysts for C-C and C-X bond formation with aryl bromide and chloride substrates. In the second half, novel applications of phosphine-functionalised polymers as reagents, scavengers, organocatalysts and linkers in organic chemistry are presented. Emphasis is placed on the synthesis of biologically active molecules.     

Cycloaddition Reactions and Dendritic Polymer Architectures – A Perfect Match

Summery: The potential of cycloaddition (CA) reactions for the synthesis of dendritic polymers is pointed out. The [4 + 2] Diels Alder cycloaddition as well as 1,3-dipolar CA reactions including “click chemistry” are addressed, and the advantages of these reactions like high selectivity, thus high tolerance towards additional functionalities, high yields and synthesis under mild reaction conditions are highlighted. New perfectly branched dendrimers as well as hyperbranched polymers have been prepared and modified using the 1,3-dipolar cycloaddition reaction of azines with alkynes. The 1,3-dipolar CA reaction of bisazine with maleimides results in hyperbranched and thus, irregular and broadly distributed polymers though with a degree of branching of 100% due to special intermediate formation. The [4 + 2] Diels Alder cycloaddition was successfully applied for the synthesis of highly branched polyphenylene structures using the AB₂ + AB and the A₂ + B₃ approach. CA reactions are also very suitable for highly efficient polymer analogous reactions and thus, they can also be used to prepare complex polymer architectures like dendronized polymers.     

Topological polymer chemistry by dynamic selection from electrostatic polymer self-assembly

A collection of recent developments in topological polymer chemistry is presented. First, topological isomerism occurring on randomly coiled, flexible polymer molecules having cyclic and linear structures is discussed. Second, an electrostatic self-assembly and covalent fixation strategy has been developed for the synthesis of polymeric topological isomers. These isomers have double cyclic, manacle-, and theta-shaped constructions, and are prepared by using either linear or star telechelic polymer precursors having moderately strained cyclic ammonium salt groups, which carry multifunctional carboxylate counteranions. A technique of reversed-phase chromatography (RPC) is demonstrated as an effective means to separate polymers with different topologies, especially polymeric topological isomers. A further extension of topological polymer chemistry has been observed by dynamic selection from electrostatic polymer self-assembly to enable the effective formation of tadpole-shaped, cyclic-linear hybrid topologies.     

Cyclic Polymers by Ring‐Closure Strategies

The preparation of cyclic macromolecules has always represented a challenging task for polymer science, mainly because of difficulties in connecting chain extremities together. Initiated by the pioneering studies of Jacobson and Stockmayer, preparative pathways to cyclic polymers have been considerably improved within the last two decades thanks to the advent of both controlled polymerizations and efficient coupling reactions in organic chemistry. This Review aims to provide a critical up‐to‐date overview and illustrate the considerable efforts that have been made in the past few years to improve the availability of macrocycles for industrial and academic investigations through the use of the ring‐closure approach. Particular attention is paid to methods for the preparation of monocycles over more complex architectures, since the latter are usually derived from the former.     

选择性催化混合单体制备多组分聚酯的研究进展

以聚乳酸和聚碳酸酯等为代表的生物可降解高分子材料已被应用于包装材料和生物医用等领域.然而受链段结构的影响,这类均聚物材料在实际应用中受到了一定限制.将不同性质聚合物链段通过共价键连接形成的嵌段共聚物具有组分均匀、性能可控等优点,是优化材料性能的一种方法.本文概述了环酯、环氧化物和CO2(或环状酸酐)的多元共聚反应合成嵌...     

A Simple and Versatile Method for the Construction of Nearly Ideal Polymer Networks

Polymer networks usually contain numerous inhomogeneities that deteriorate their physical properties and should be eliminated to create reliable, high‐performance materials. A simple method is introduced for the production of nearly ideal networks from various vinyl polymers through controlled polymerization and subsequent crosslinking. Monodisperse star polymers with bromide end groups were synthesized by atom‐transfer radical polymerization and end‐linked with dithiol linkers using thiol–bromide chemistry. This simple procedure formed nearly ideal polymer networks, as revealed from elasticity of the formed gel and model conjugation reactions involving linear polymers. The versatility of this method was demonstrated by preparing networks of common vinyl polymers, including polyacrylates, polymethacrylate, and polystyrene. This method can be used to prepare multiple functional nearly ideal gels and elastomers and to explore fundamental aspects of polymer networks.     

超分子构筑调控合成结构规整的梯形聚合物及其应用研究

综述了"超分子构筑调控的逐步偶联/聚合法",该方法将高分子化学与超分子化学相结合,利用多种类型的超分子弱键协同作用首先构筑预期的梯形超分子结构,再经聚合得到共价键梯形高分子.利用该方法合成了一系列结构规整的氧桥基和有机桥基梯形聚硅氧烷以及碳基梯形聚酯,并利用侧基间π-π叠加作用实现了对聚合物立体构型控制.扼要介绍了梯形聚合物在先进材料方面的应用,例如梯形聚硅氧烷液晶光致取向膜;由梯形聚硅氧烷合成的管状聚硅氧烷在高室温储存期微电子环氧塑封料方面的应用;以及基于梯形聚硅氧烷的拟筛板聚合物在二阶非线性光学材料方面的应用等.     

Recent progress on cyclic polymers: Synthesis,bioproperties, and biomedical applications

Polymer topologies exert a significant effect on its properties, and polymer nanostructures with advanced architectures, such as cyclic polymers, star‐shaped polymers, and hyperbranched polymers, are a promising class of materials with advantages over conventional linear counterparts. Cyclic polymers, due to the lack of polymer chain ends, have displayed intriguing physical and chemical properties. Such uniqueness has drawn considerable attention over the past decade. The current review focuses on the recent progress in the design and development of cyclic polymer with an emphasis on its synthesis and bio‐related properties and applications. Two primary synthetic strategies towards cyclic polymers, that is, ring‐expansion polymerization and ring‐closure reaction are summarized. The bioproperties and biomedical applications of cyclic polymers are then highlighted. In the end, the future directions of this rapidly developing research field are discussed. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 1447–1458     

Enantio‐, Regio‐, and Chemoselective Lipase‐Catalyzed Polymer Synthesis

In contrast to chemical routes, enzymatic polymerization possesses favorable characteristics of mild reaction conditions, few by‐products, and high activity toward cyclic lactones which make it a promising technique for constructing polymeric materials. Meanwhile, it can avoid the trace residue of metallic catalysts and potential toxicity, and thus exhibits great potential in the biomedical fields. More importantly, lipase‐catalyzed polymer synthesis usually shows favorable enantio‐, regio‐, and chemoselectivity. Here, the history and recent developments in lipase‐catalyzed selective polymerization for constructing polymers with unique structures and properties are highlighted. In particular, the synthesis of polymeric materials which are difficult to prepare in a chemical route and the construction of polymers through the combination of selective enzymatic and chemical methods are focused. In addition, the future direction is proposed especially based on the rapid developments in computational chemistry and protein engineering techniques.     

Renaissance of immobilized catalysts. New types of polymer-supported catalysts, 'microencapsulated catalysts', which enable environmentally benign and powerful high-throughput organic synthesis

Immobilized catalysts have been reinvestigated from two aspects; as keys to environmentally benign chemical processes and high-throughput organic synthesis for combinatorial chemistry. While most known polymer-supported catalysts are less active than the corresponding original catalysts, new types of polymer-supported catalysts, microencapsulated catalysts, have been developed. The catalysts were immobilized on to polymers using physical envelopment by polymer backbones and interaction between pi electrons of benzene rings of the polystyrenes used as polymer backbones and vacant orbitals of the catalysts. Microencapsulated Sc, Os, Pd and Ru catalysts have been successfully prepared and high activities have been attained. In all cases, no leaching of the catalysts occurred, and the immobilized catalysts were recovered quantitatively by simple filtration and reused without loss of activity. It is noted that this method enables direct immobilization of metals onto polymers, and that normally unstable species such as Pd(0)(PPh3) can be kept stable by this immobilization technique. It is expected that other metal catalysts can be immobilized using this microencapsulation technique.     

Opportunities In Interfacial Area Between Organic and Materials Chemistry

It is well recognized that the current trend in organic chemistry is diverged into two frontiers: biochemistry and materials chemistry. This talk presents our recent research effort in the interfacial area between organic and materials chemistry. The major theme of our research is focused upon the rational design, synthesis and characterization of novel functional and multifunctional polymers and molecules. Typical examples of current projects are: 1). Development of polymerization methodologies: a). exploration of palladium catalyzed reactions for polycondensations, b). living ring-opening polymerization of cyclic lactone to form thioester-functionalized polyesters for chemo-ligation, 2). Design, synthesis and physical studies of photorefractive polymers, 3). Second order nonlinear optical polymers, 4). Conjugated diblock polymers for the formation of self-assembled, nano-sized electroactive materials, 5). High-performance light emitting diodes from new conjugated polymers, 6). Conjugated liquid crystalline polymers, 7). Architectural controls of polymer microstructures, including synthesis of dendritic polyphenylenevinylenes, 8). Metal-containing functional polymers. 9) Biocompatible polymers.     

Nitroxides: applications in synthesis and in polymer chemistry

This Review describes the application of nitroxides to synthesis and polymer chemistry. The synthesis and physical properties of nitroxides are discussed first. The largest section focuses on their application as stoichiometric and catalytic oxidants in organic synthesis. The oxidation of alcohols and carbanions, as well as oxidative C-C bond-forming reactions are presented along with other typical oxidative transformations. A section is also dedicated to the extensive use of nitroxides as trapping reagents for C-centered radicals in radical chemistry. Alkoxyamines derived from nitroxides are shown to be highly useful precursors of C-centered radicals in synthesis and also in polymer chemistry. The last section discusses the basics of nitroxide-mediated radical polymerization (NMP) and also highlights new developments in the synthesis of complex polymer architectures.     

基于C–H活化的炔烃聚合反应合成多功能稠(杂)环聚合物

稠(杂)环聚合物是一类重要的功能聚合物,因其优异的光电特性而被广泛应用于光电领域.这类聚合物的传统制备方法往往需要用到修饰有复杂官能团的稠(杂)环单体,这些单体种类有限且合成难度大,导致稠(杂)环聚合物的发展受到限制. C–H活化过程的发现与提出为利用惰性的C–H键作为潜在官能团提供了可能,有效避免了对单体进行复杂修饰的要求,大大扩增了单体的种类和来源.基于C–H活化的炔烃环化聚合反应,能够在聚合物骨架中原位直接形成稠(杂)环结构,具有原料简单易得、聚合效率高、产物结构丰富等诸多优势,因此受到广泛关注.本文分类总结了基于C–H活化的炔烃环化聚合领域的最新进展,包括合成手段和所得聚合物的性质与功能介绍,并对该领域的未来发展方向进行了展望.