Polymerized Ionic Liquids (Smart Materials, 29, Band 29) - Hardcover

 
9781782629603: Polymerized Ionic Liquids (Smart Materials, 29, Band 29)
Hardcover
ISBN 10: 1782629602 ISBN 13: 9781782629603
Verlag: Royal Society of Chemistry, 2017

Inhaltsangabe

The applications of ionic liquids can be enormously expanded by arranging the organic ions in the form of a polymer architecture. Polymerized ionic liquids (PILs), also known as poly(ionic liquid)s or polymeric ionic liquids, provide almost all features of ionic polymers plus a rare versatility in design. The mechanical properties of the solid or solid-like polymers can also be controlled by external stimuli, the basis for designing smart materials.

Known for over four decades, PILs are a member of the ionic polymers family. Although the previous forms of ionic polymers have a partial ionicity, PILs are entirely composed of ions. Therefore, they offer a better flexibility for designing a responsive architecture as smart materials. Despite the terminology, PILs can be synthesized from solid organic ionic salts since the monomer liquidity is not a requirement for the polymerization process. Ionicity can also be induced to a neutral polymer by post-polymerization treatments.

This is indeed an emerging field whose capabilities have been somehow overshadowed by the popularity of ionic liquids. However, recent reports in the literature have shown impressive potentials for the future. Written by leading authors, the present book provides a comprehensive overview of this exciting area, discussing various aspects of PILs and their applications as smart materials. Owing to the novelty of this area of research, the book will appeal to a broad readership including students and researchers from materials science, polymer science, chemistry, and physics.

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Über die Autorin bzw. den Autor

Åbo Akademi University, Sweden

Von der hinteren Coverseite

The applications of ionic liquids can be enormously expanded by arranging the organic ions in the form of a polymer architecture. Polymerized ionic liquids (PILs), also known as poly(ionic liquid)s or polymeric ionic liquids, provide almost all features of ionic polymers plus a rare versatility in design. The mechanical properties of the solid or solid-like polymers can also be controlled by external stimuli, the basis for designing smart materials.

Known for over four decades, PILs are a member of the ionic polymers family. Although the previous forms of ionic polymers have a partial ionicity, PILs are entirely composed of ions. Therefore, they offer a better flexibility for designing a responsive architecture as smart materials. Despite the terminology, PILs can be synthesized from solid organic ionic salts since the monomer liquidity is not a requirement for the polymerization process. Ionicity can also be induced to a neutral polymer by post-polymerization treatments.

This is indeed an emerging field whose capabilities have been somehow overshadowed by the popularity of ionic liquids. However, recent reports in the literature have shown impressive potentials for the future. Written by leading authors, the present book provides a comprehensive overview of this exciting area, discussing various aspects of PILs and their applications as smart materials. Owing to the novelty of this area of research, the book will appeal to a broad readership including students and researchers from materials science, polymer science, chemistry, and physics.

Aus dem Klappentext

The applications of ionic liquids can be enormously expanded by arranging the organic ions in the form of a polymer architecture. Polymerized ionic liquids (PILs), also known as poly(ionic liquid)s or polymeric ionic liquids, provide almost all features of ionic polymers plus a rare versatility in design. The mechanical properties of the solid or solid-like polymers can also be controlled by external stimuli, the basis for designing smart materials.

Known for over four decades, PILs are a member of the ionic polymers family. Although the previous forms of ionic polymers have a partial ionicity, PILs are entirely composed of ions. Therefore, they offer a better flexibility for designing a responsive architecture as smart materials. Despite the terminology, PILs can be synthesized from solid organic ionic salts since the monomer liquidity is not a requirement for the polymerization process. Ionicity can also be induced to a neutral polymer by post-polymerization treatments.

This is indeed an emerging field whose capabilities have been somehow overshadowed by the popularity of ionic liquids. However, recent reports in the literature have shown impressive potentials for the future. Written by leading authors, the present book provides a comprehensive overview of this exciting area, discussing various aspects of PILs and their applications as smart materials. Owing to the novelty of this area of research, the book will appeal to a broad readership including students and researchers from materials science, polymer science, chemistry, and physics.

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Polymerized Ionic Liquids

By Ali Eftekhari

The Royal Society of Chemistry

Copyright © 2018 The Royal Society of Chemistry
All rights reserved.
ISBN: 978-1-78262-960-3

Contents

Chapter 1 Polymerization in Ionic Liquids Nikhil K. Singha, Kunlun Hong and Jimmy W. Mays, 1, 
Chapter 2 Porous Ionic Liquid Materials Alessandro Dani, Valentina Crocella, Giulio Latini and Silvia Bordiga, 23, 
Chapter 3 Cationic and Anionic Polymerized Ionic Liquids: Properties for Applications Olga Kuzmina, 83, 
Chapter 4 Switchable Hydrophobicity and Hydrophilicity Yuki Kohno and Hiroyuki Ohno, 117, 
Chapter 5 Switchable Polarity Liquids S. G. Khokarale, I. Anugwom, P Maki-Arvela, P Virtanen and J.-P. Mikkola, 143, 
Chapter 6 Stimuli Responsive Smart Fluids Based on Ionic Liquids and Poly(ionic liquid)s Jianbo Yin, Qi Lei, Yuezhen Dong and Xiaopeng Zhao, 180, 
Chapter 7 Thermo-responsive Poly(ionic liquid) Nanogels Prepared via One-step Cross-linking Copolymerization J. R. Yu, Y. Zuo and Y. B. Xiong, 202, 
Chapter 8 Redox-active Immobilized Ionic Liquids and Polymer Ionic Liquids Thuan-Nguyen Pham-Truong, Jalal Ghilane and Hyacinthe Randriamahazaka, 225, 
Chapter 9 Doping Polymers with Ionic Liquids to Manipulate Their Morphology and Membrane Gas Separation Properties Xianda Hou, Junyi Liu, Hien Nguyen and Haiqing Lin, 262, 
Chapter 10 Ionic Liquid-modified Poly(Vinylidene Fluoride): from High Performance Anti-static Materials to Flexible Dielectric Materials C. Y. Xing and Y. J. Li, 280, 
Chapter 11 Ionic Liquids as Tools in the Production of Smart Polymeric Hydrogels S. S. Silva and R. L. Reis, 304, 
Chapter 12 Preparation of Functional Polysaccharides and Related Materials Combined with Ionic Liquids J. Kadokawa, 319, 
Chapter 13 Tailoring Transport Properties Aiming for Versatile Ionic Liquids and Poly(Ionic Liquids) for Electrochromic and Gas Capture Applications Roberto M. Torresi, Cintia M. Corrêa, Tânia M. Benedetti and Vitor L. Martins, 342, 
Chapter 14 Wearable Energy Storage Based on Ionic Liquid Gels Stephanie F. Zopf, Anthony J. D'Angelo, Huan Qin and Matthew J. Panzer, 381, 
Chapter 15 Ionic Liquids in Wearable Chemical Sensors S. A. Goodchild, M. R. Sambrook and A. J. S. McIntosh, 416, 
Chapter 16 Ionic Electrochemical Actuators A. Maziz, A. Simaite and C. Bergaud, 456, 
Chapter 17 Capturing CO2 with Poly(Ionic Liquid)s S. Einloft, F. L. Bernard and F. Dalla Vecchia, 489, 
Chapter 18 Ionic Liquid-based Polymers and Crystals for Dye-sensitized Solar Cells Chuan-Pei Lee and Kuo-Chuan Ho, 515, 
Subject Index, 531,


CHAPTER 1

Polymerization in Ionic Liquids

NIKHIL K. SINGHA, KUNLUN HONG AND JIMMY W. MAYS


Introduction

Most liquids used as solvents are composed of neutral molecules. In contrast, ionic liquids (ILs) are salts in the liquid state at ambient or near ambient temperatures. This room temperature ionic liquid state is often achieved by choosing ion pairs where one is organic and has a delocalized charge, or by choosing bulky asymmetric substituents. This causes the ions to be poorly coordinated, resulting in low melting temperatures. In principle, literally millions of ionic liquids with an exceptionally wide range of properties can be produced. This has led to ILs being considered as designer solvents or task specific solvents, where their extremely low vapor pressures offer potential to minimize pollution associated with volatile organic compound (VOC) solvents through recycling.

Some examples of common IL cations and anions and their general characteristics are shown in Figure 1.1. Imidazolium- and pyridinium-based ILs feature delocalized cations, whereas quaternary ammonium cations are asymmetrically substituted. A very wide range of properties, including viscosity, hydrophobicity or hydrophilicity, thermal and chemical stability, melting point, flammability and cost, can be tuned by judicious selection of the cation and anion.

Probably the first room temperature IL, ethylammonium nitrate (m.p. 12 °C), was reported by Walden in 1914. However, there was little interest in ILs until the mid-1970s when they attracted attention as electrolytes for batteries. Nowadays, ILs are being intensely investigated in a wide range of applications, including use as solvents in a wide range of chemical processes. ILs have been used as solvents for Diels-Alder reactions, hydrogenations, alkylations, Friedel-Crafts reactions, Heck reactions, Suzuki couplings, metathesis reactions,^ and many others.

To the best of our knowledge, the first polymerization in ILs was reported in 1990 by Carlin et al. They reported that TiCl4 and AlEthylCl in AlCl3/1-ethyl3-methylimmidazolium chloride ([EMIM]Cl) could polymerize ethylene in low yields. Subsequent work by the same group, where TiCl4 was replaced by Cp2TiCl2, gave higher yields. This pioneering work, using ILs as a reaction medium for polymerization, has inspired numerous researchers over the past quarter of a century to investigate a wide range of different types of polymerization in ILs. While much of this work was inspired by the "green" aspects of ionic liquids (very low vapor pressure and potential for recycling), it quickly became apparent that chemistry could often proceed differently (faster polymerization rates, higher molecular weights, enhanced yields, etc.) in ILs. Providing a review of the field of polymerization in ionic liquids, with particular attention to developments over the past several years, is the subject of this chapter. The reader is referred to earlier reviews in this field for additional details on work in this area.


ILs in Conventional Free Radical Polymerization

Free radical polymerization, because of its compatibility with a wide range of monomers having different types of functional groups, is one of the most widely used polymerization techniques. Free radical solution polymerization is of great commercial importance as dilution of radical polymerizations with a solvent, typically a VOC, is effective in controlling viscosity and the exotherm accompanying polymerization. Hong et al. noted large increases in the rate of polymerization and much higher molecular weights for free radical polymerization of methyl methacrylate (MMA) in [BMIM]PF6 as compared to polymerizations carried out under identical conditions in VOCs. These effects were attributed at least in part to the high viscosity of the polymerization medium. A "diffusion-controlled termination" mechanism was proposed to explain the decreased rate of chain termination in these viscous systems. A decrease in termination rate could explain a simultaneous increase in the rate of polymerization and molecular weight. In contrast to variations in the rate of polymerization and molecular weight, the polymers synthesized in RTILs have similar glass transition temperatures and microstructures as compared to those obtained in benzene or in bulk, based upon thermal analysis and 13C-NMR experiments. Since then, other groups have reported similar behavior, high molecular weights and rapid polymerization rates, for MMA and other methacrylates in [BMIM]pF6. Harrison et al. used pulse laser polymerization (PLP) techniques to polymerize MMA in [BMIM]pF. They found that both the propagation and termination rates, kp and kt, respectively, were strongly affected by the presence of [BMIM]PF6. They attributed the increase in propagation rate to the high polarity of the ionic liquid solution, which reduces the activation energy of propagation...

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Verlag
Royal Society of Chemistry
Erscheinungsdatum
2017
Sprache
Englisch
ISBN 10 
1782629602
ISBN 13 
9781782629603
Einband
Gebundene Ausgabe
Anzahl der Seiten
541
Herausgeber
Eftekhari Ali
Kontakt zum Hersteller
Nicht verfügbar
Verantwortliche Person
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