Coupled Electrical Conduction in Coordination Polymers: From Electrons/Ions to Mixed Charge Carriers

The coupled transport of ions and electrons is of great potential for next‐generation sensors, energy storage and conversion devices, optoelectronics, etc. Coordination polymers (CPs) intrinsically have both transport pathways for electrons and ions, however, the practical conductivities are usually low. In recent years, significant advances have been made in electronic or ionic conductive coordination polymers, which also results in progress in mixed ionic‐electronic conductive coordination polymers. Here we start from electronic and ionic conductive CPs to mixed ionic‐electronic conductive CPs. Recent advances in the design of mixed ionic‐electronic conductive CPs are summarized. In addition, devices based on mixed conduction are selected.     

Extrusion 3D printing of conjugated polymers

Conjugated polymers combine electronic charge transport properties with the ability to transport ions, enabling transduction between ionic and electronic currents. Many applications of conjugated polymers, such as biointerfaces, actuators, and energy storage, benefit from 3D structures. Among different methods for 3D fabrication, extrusion-based 3D printing is a versatile approach that is compatible with multimaterial fabrication processes. This review summarizes progress in the emerging field of 3D printed conjugated polymers using three extrusion printing processes: direct ink write, meniscus-guided printing, and electrohydrodynamic printing. Ink designs for direct in write are described in depth, including strategies for modifying the rheology and conductivity of the inks.     

芳杂环高分子

本文简要介绍芳杂环高分子进展及其在高科技工业中的应用概况。     

Recent advances in conjugated polymer energy storage

This review covers recent advances in conjugated polymers and their application in energy storage. Conjugated polymers are promising cost-effective, lightweight, and flexible electrode materials. The operating principles of conjugated polymers are presented within the framework of their potential for energy storage. Special focus is given to polyaniline electrodes. Recent advances are reviewed including new methods of synthesis, nanostructuring, and assembly. Also, covered are applications that take full advantage of the mechanical properties of conjugated polymers and future applications of these novel materials. © 2013 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2013     

Conformation Control of Conjugated Polymers

In the past few decades, conjugated polymers have aroused extensive interest in organic electronic applications. The electrical performance of conjugated polymers has a close relationship with their backbone conformation. The conformation of the polymer backbone strongly affects the πelectron delocalization along polymer chains, the energy band gap, interchain interactions, and further affects charge transport properties. To realize a rigid coplanar backbone that usually possesses efficient intrachain charge transport properties and enhanced π–π stackings, such conformation control becomes a useful strategy to achieve high-performance (semi)conducting polymers. This minireview summarizes the most important polymer structures through conformation control at the molecular level, and then divides these rigid coplanar conjugated polymers into three categories: 1) noncovalent interactions locked conjugated polymers; 2) double-bond linked conjugated polymers; 3) ladder conjugated polymers. The effect of the conformation control on physical nature, optoelectronic properties, and their device performance is also discussed, as well as the challenges of chemical synthesis and structural characterization.     

金属纳米粒子/聚合物体系的稳定性及其机理

金属纳米粒子由于其小的尺寸和大的比表面积等特点,使其具有独特的热性能、电性能、磁性能和光性能,以及很强的团聚趋势。因此金属纳米粒子是否被稳定在纳米尺度内,是它们能否表现出独特性能的关键。本文综述了非离子聚合物、聚电解质、两亲聚合物、双亲水聚合物、树状聚合物对金属纳米粒子的稳定作用及其稳定机理的研究进展。     

Recent theories of gas sorption in polymers

Theories and models are presented for gas sorption in polymers above and below the glass transition temperature. With the exception of predictive theories that do not represent the data well, the models are fit to data for the carbon dioxide/silicone rubber and carbon dioxide/polycarbonate systems for the purposes of comparison. During the past decade, a number of new models and theories have been proposed specifically for gas sorption in glassy polymers. Each new model attempts to incorporate aspects of the gas sorption process that are unique to polymers below the glass transition temperature. This review discusses these recent advances, the assumptions used in their development and their advantages and disadvantages.     

金属纳米粒子/聚合物体系的稳定性及其机理

金属纳米粒子由于其小的尺寸和大的比表面积等特点,使其具有独特的热性能、电性能、磁性能和光性能,以及很强的团聚趋势。因此金属纳米粒子是否被稳定在纳米尺度内,是它们能否表现出独特性能的关键。本文综述了非离子聚合物、聚电解质、两亲聚合物、双亲水聚合物、树状聚合物对金属纳米粒子的稳定作用及其稳定机理的研究进展。     

Polymers and the Periodic Table: Recent Developments in Inorganic Polymer Science

Polysiloxanes [? R₂Si? O? ]_n, polyphosphazenes [? R₂P?N? ]_n, and polysilanes [? R₂Si? ]_n illustrate that the incorporation of inorganic elements into a polymer main chain can lead to useful properties. These include low temperature flexibility, high thermal and oxidative stability, flame retardancy, novel forms of chemical reactivity, and intriguing electrical and optical characteristics arising from unusual electronic effects such as the delocalization of σ electrons. However, until recently, the development of inorganic polymer science has been held back by the synthetic problem of finding ways to join atoms of inorganic elements together into long chains. This review surveys many of the exciting advances in the field of inorganic polymers over the past decade and focuses mainly on the new inorganic polymer systems that have been prepared during this period. These include random-network polysilynes, poly(carbophosphazene)s, sulfur–nitrogen–phosphorus polymers, poly(organooxothiazene)s, and, very recently, the first examples of polystannanes that possess a main chain of tin atoms. Transition metal based polymer science has also experienced a number of synthetic break-throughs and new materials include high molecular weight metallocene-based polymers, polymetallaynes incorporating elements such as iron, nickel, and rhodium, liquid crystalline organocobalt and organochromium polymers, and lanthanide-based polymers.     

全共轭型二茂铁基聚合物

由于二茂铁独特的夹心结构使含二茂铁基聚合物具有独特的电、磁、催化以及氧化还原性能。全共轭型二茂铁基聚合物由于其特殊的π-π电子结构,使其在电学、光学等方面的表现出优越的性质。本文从3个方面（主链型、侧链型和超支化型）介绍了近年来含有二茂铁基团全共轭聚合物的合成及其性能方面的研究进展,讨论了聚合物的结构对溶解性、氧化还原性等方面的影响,并探讨了这一领域存在的问题及可能的发展方向。     

“Smart” Polymers: Physicochemical Characteristics and Applications in Bio-Separation Strategies

In recent years, smart polymers (SPs), which are also referred to as bio-responsive polymers, have gained considerable attention as a unique class of polymers and their applications have been increasing significantly. These so-called “smart” polymers, either synthetic or biological, have been defined as “polymers designed to respond or undergo physical and structural conformational changes/rearrangement in response to slight changes in their surrounding environment”. They are categorized as thermo-, pH-, electro- and magneto-responsive polymers. The advances in upstream bio-production stages and the high cost associated with downstream chromatographic techniques have pushed the development of new alternatives. In this context, the use of SPs, in combination with non-chromatographic technologies, represents a useful approach to the development of new downstream operation units. With the key scientific advancements, SPs have become the “next generation” of the bio-separation tool for eco-friendlier and cost-effective purification. This review describes the different characteristics and classifications of various “smart” polymers available for use in bio-separation strategy. Focus is also given to the recent advances in SP inclusion in the improvement of alternative non-chromatographic methods in downstream bioprocessings.     

开环易位聚合合成瓶刷聚合物

瓶刷聚合物是一类具有独特侧链结构的梳形聚合物。功能性瓶刷聚合物在光子晶体、表面活性剂、医药载体、防污涂层以及智能材料等领域具有良好的应用价值。通过开环易位聚合合成瓶刷聚合物的方法具有合成步骤简单、聚合物接枝密度高和侧链组成均一等优点,在控制聚合物组成、分子量和分散性等方面具有显著优势。本文基于开环易位聚合,简述了合成瓶刷均聚物以及嵌段型、混合型和核-壳型三种类型的瓶刷共聚物的方法,并介绍了合成精确结构的瓶刷聚合物的新进展。     

Trends in Structural Polymer Science in Industry

Plastics production has grown rapidly in the past 30 years. The versatility of plastics which is not exceeded by any other class of materials, guarantees that polymers will continue to be very important in the future. However, at present a distinct change is taking place in polymer research and development. While in the pioneering days of plastics new polymer properties were determined by the choice of suitable monomers, today the commercialization of polymers from new monomers is restricted to a few specialities with a rather modest production volume. On the other hand, the number of new polymers derived from old monomers is increasing very rapidly. The development of highly selective catalysts and advances in reactor technology have provided the means for producing new tailor-made polymers. The same is true regarding new polymer blends and alloys based on old polymers: blending immiscible polymers yields materials with property profiles superior to the features of the individual components. Using selected examples, this paper will discuss trends, possibilities and challenges for structural polymer research in industry. © 1997 John Wiley & Sons, Ltd.     

Dispersion of Polymers in Metallic Gallium

This work examines the concept of dispersing polymers in metals. Herein, this was mainly studied with molten gallium, in which 5‐18 wt % of various short‐chain polymers were incorporated and mixed. The nature of the solidified products was examined by using X‐ray diffraction, electron microscopy, UV/Vis, differential scanning calorimetry, and thermal gravimetric analyses. It was found that some polymers can be dispersed as small domains within molten metals to form a heterogeneous solid. The ability to dope Ga with large polymers opens a new avenue to electronic materials.     

Transition-metal-templated synthesis of rotaxanes and catenanes: From small molecules to polymers

This article provides an overview of the fundamental principles of the synthesis of metallocatenanes and metallorotaxanes. It also describes the synthesis and properties of electronic conducting polymers—polypyrrole and polythiophene—built around metallocatenanes and metallorotaxanes. The particular properties of this new class of polymers, including the possibility of transmetallation reactions being performed with them and the observation of electronic coupling between the metal centers and the conducting matrix, are discussed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3470–3477, 2003     

Metal-containing conjugated oligo- and polythiophenes

Conjugated polymers containing metal groups are an important class of new materials that may find application as sensors, non-linear optical materials and in molecular electronics. Polythiophenes are an extensively studied class of conjugated polymers, that can be easily modified synthetically, and may be prepared using a variety of methods. Metal groups pendant to polythiophene backbones modulate the electronic, optical and redox properties of the conjugated backbone and can introduce novel structural motifs to these materials. Functionalization of oligo- and polythiophenes by Fe, Pd and Ru containing groups is discussed, along with the properties of some of these materials.     

Conjugated Polymers: Catalysts for Photocatalytic Hydrogen Evolution

Conjugated polymers, comprising fully π‐conjugated systems, present a new generation of heterogeneous photocatalysts for solar‐energy utilization. They have three key features, namely robustness, nontoxicity, and visible‐light activity, for photocatalytic processes, thus making them appealing candidates for scale‐up. Presented in this Minireview, is a brief summary on the recent development of various promising polymer photocatalysts for hydrogen evolution from aqueous solutions, including linear polymers, planarized polymers, triazine/heptazine polymers, and other related organic conjugated semiconductors, with a particular focus on the rational manipulation in the composition, architectures, and optical and electronic properties that are relevant to photophysical and photochemical properties. Some future trends and prospects for organic conjugated photocatalysts in artificial photosynthesis, by water splitting, are also envisaged.     

Synthesis,characterization and application of soluble fullerenated polymer materials

This article only deals with the topic of intense interest to us and to a considerable extent of our own experimental results on the synthesis,characterization and application of C60-con-taining functional polymers such as poly(N-vinylcarbazole),polystyrene and polyacrylonitrile-based fullerene polymers.The results demonstrate that [60] fullerene can be directly incorporated into a variety of functional polymers by copolymer-ization or grafting,but also can be used to modify or improve the electronic,optical and physicochemical properties of polymers.Both the stereo-electroniceffect and the steric hindrance of C60 have an important influence on the structure and physicochemical properties of the parent polymer.     

Impact of the anion on electrochemically doped regioregular and regiorandom poly(3-hexylthiophene)

Chemical and electrochemical doping of π-conjugated polymers is an important aspect in determining the performance and enabling the operation of many organic electronic devices, from organic light emitting diodes and thermoelectrics to organic electrochemical transistors. In both chemical doping and electrochemical doping an ionized dopant or counterion is present along with the doped π-conjugated polymer. This dopant or counterion is not a benign spectator, rather, its presence can significantly impact the optical, electronic, and thermoelectric properties of the resulting material. Here, we investigate how counterion structure impacts the electrochemical doping ability, oxidation potential, ionization energy, and polaron absorbance of regioregular (rr) and regiorandom (rra) P3HT. We find that in most cases the anion has a small effect on the polymer oxidation potential, except for in the case of rr-P3HT with the large tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anion. We propose that this large anion is excluded from the crystalline regions and thus the oxidation potential is similar to that of rra-P3HT. The anions also result in significant differences in polaron absorbance and ionization energies, thereby emphasizing the important role of the counterion in determining the optical and electronic properties of doped π-conjugated polymers.     

氮杂环高分子化合物的电催化性能进展

介绍了氮杂环高分子配合物及其电催化性能,归纳了含氮杂环高分子配合物的结构类型及其在界面上的自组装过程,分析了氮杂环高分子自组装膜表面化学反应的特性。对自组装技术制备超薄层材料及表面改性技术在分子电子器件等方面的应用作了评述。