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Ionic Systems in Polymer Science: Ionic Liquids and Ionic Polymers for the Development of Novel Materials, Processes, and Applications

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A special issue of Polymers (ISSN 2073-4360). This special issue belongs to the section "Polymer Chemistry".

Deadline for manuscript submissions: closed (31 May 2019) | Viewed by 25020

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Special Issue Editors

Dr. Carlos Guerrero Sanchez

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Guest Editor

1. Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Jena, Germany
2. Jena Center for Soft Matter (JCSM), Friedrich Schiller University Jena, Jena, Germany
Interests: Ionic liquids; polymer recycling; reversible deactivation radical polymerizations; ionic polymerizations; high-throughput experimentation; self-assembly of polymers; drug delivery systems
Special Issues, Collections and Topics in MDPI journals

Dr. Tamar Greaves

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Guest Editor

School of Science, RMIT University, Melbourne, VIC 3000, Australia
Interests: Ionic liquids; protic ionic liquids; self-assembly; SAXS; liquid crystals; high throughput
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

Polymer science has seen impressive development during the last few decades, with the advent of ionic and reversible deactivation radical polymerization techniques allowing for an unprecedented control over macromolecular properties and architectures. With these modern synthetic tools, polymer science is currently able to provide practically unlimited polymers to intensively cooperate with other chemical, physical, and biological sciences in order to better understand fundamental phenomena or to develop novel applications. This multidisciplinary work has the main purpose of delivering environmentally-friendly, sustainable, safer, more efficient, and/or less expensive materials suitable for specific applications and processes for their manufacture. Within this context, it is believed that ionic interactions between polymers and other chemical moieties play a crucial role for the aforementioned purposes. Hence, this Special Issue focuses on fundamental phenomena and practical applications derived from different ionic interactions in polymer science. In particular, this Special Issue emphasizes on the exploitation of ionic liquids and/or ionic polymers for the development of novel materials, processes, and/or applications that might certainly have a positive influence on the continuous quest for new and better materials for different fields of science and technology.

Dr. Carlos Guerrero Sanchez
Dr. Tamar Greaves
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Polymers is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

Ionic liquids
Self-assembly of polymers in ionic liquids
Cationic polymers
Anionic polymers
Green polymerization processes in ionic liquids

Published Papers (5 papers)

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Research

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25 pages, 3859 KiB

Open AccessArticle

Rheology of Concentrated Polymer/Ionic Liquid Solutions: An Anomalous Plasticizing Effect and a Universality in Nonlinear Shear Rheology

by Zhonghua Liu, Wei Wang, Florian J. Stadler and Zhi-Chao Yan

Polymers 2019, 11(5), 877; https://doi.org/10.3390/polym11050877 - 14 May 2019

Cited by 7 | Viewed by 4763

Abstract

An anomalous plasticizing effect was observed in polymer/ionic liquid (IL) solutions by applying broad range of rheological techniques. Poly(ethylene oxide)(PEO)/IL solutions exhibit stronger dynamic temperature dependence than pure PEO, which is in conflict with the knowledge that lower-T_g solvent increases the fractional free volume. For poly(methy methacrylate)(PMMA)/IL solutions, the subtle anomaly was detected from the fact that the effective glass transition temperature T_g,eff of PMMA in IL is higher than the prediction of the self-concentration model, while in conventional polymer solutions, T_g,eff follows the original Fox equation. Observations in both solutions reveal retarded segmental dynamics, consistent with a recent simulation result (Macromolecules, 2018, 51, 5336) that polymer chains wrap the IL cations by hydrogen bonding interactions and the segmental unwrapping delays their relaxation. Start-up shear and nonlinear stress relaxation tests of polymer/IL solutions follow a universal nonlinear rheological behavior as polymer melts and solutions, indicating that the segment-cation interaction is not strong enough to influence the nonlinear chain orientation and stretch. The present work may arouse the further theoretical, experimental, and simulation interests in interpreting the effect of complex polymer-IL interaction on the dynamics of polymer/IL solutions. Full article

(This article belongs to the Special Issue Ionic Systems in Polymer Science: Ionic Liquids and Ionic Polymers for the Development of Novel Materials, Processes, and Applications)

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17 pages, 2483 KiB

Open AccessArticle

Thermotropic Liquid-Crystalline and Light-Emitting Properties of Poly(pyridinium) Salts Containing Various Diamine Connectors and Hydrophilic Macrocounterions

by Tae Soo Jo, Haesook Han, Pradip K. Bhowmik, Benoît Heinrich and Bertrand Donnio

Polymers 2019, 11(5), 851; https://doi.org/10.3390/polym11050851 - 10 May 2019

Cited by 4 | Viewed by 4771

Abstract

A set of poly(pyridinium) salts containing various diamine moieties, as molecular connectors, and poly(ethyleneglycol)-4-nonylphenyl-3-sulfopropyl ether, thereafter referred to as “Macroion”, as the hydrophilic counterion, were prepared by metathesis reaction from the respective precursory tosylated poly(pyridinium)s in methanol. The structure of these ionic polymers was established by spectroscopy and chromatography techniques. The shape-persistent ionic poly(pyridinium) materials, inserting rigid or semi-rigid diamine spacers, display thermotropic liquid-crystalline properties from room-temperature up to their isotropization (in the temperature range around 160–200 °C). The nature of the LC phases is lamellar in both cases as identified by the combination of various complementary experimental techniques including DSC, POM and variable-temperature SAXS. The other polymers, inserting bulky or flexible spacers, only form room temperature viscous liquids. These new macromolecular systems can then be referred to as polymeric ionic liquid crystals (PILCs) and or polymeric ionic liquids (PILs). All the ionic polymers show excellent thermal stability, in the 260–330 °C temperature range as determined by TGA measurements, and a good solubility in common organic solvents as well as in water. Their optical properties were characterized in both solution and solid states by UV−Vis and photoluminescent spectroscopies. They emit blue or green light in both the states and exhibit a positive solvatochromic effect. Full article

(This article belongs to the Special Issue Ionic Systems in Polymer Science: Ionic Liquids and Ionic Polymers for the Development of Novel Materials, Processes, and Applications)

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18 pages, 3152 KiB

Open AccessArticle

Examining the Influence of Anion Nucleophilicity on the Polymerisation Initiation Mechanism of Phenyl Glycidyl Ether

by Fiona C. Binks, Gabriel Cavalli, Michael Henningsen, Brendan J. Howlin and Ian Hamerton

Polymers 2019, 11(4), 657; https://doi.org/10.3390/polym11040657 - 10 Apr 2019

Cited by 9 | Viewed by 3408

Abstract

The reaction of phenyl glycidyl ether (PGE) with 1-ethyl-3-methylimidazolium acetate and 1-ethyl-3-methylimidazolium thiocyanate to initiate the polyetherification reaction was examined using thermal and spectral analysis techniques. The influence of the nucleophilicity of the anions on the deprotonation of the 1-ethyl-3-methylimidazolium cation determined the reaction pathway. The thermal degradation of the ionic liquid liberated the acetate ion and led, subsequently, to the deprotonation of the acidic proton in the imidazole ring. Thus, polymerisation of PGE occurred via a carbene intermediate. The more nucleophilic thiocyanate anion was not sufficiently basic to deprotonate the 1-ethyl-3-methylimidazolium cation, and thus proceeded through direct reaction with the PGE, unless the temperature was elevated and a competing carbene mechanism ensued. Full article

(This article belongs to the Special Issue Ionic Systems in Polymer Science: Ionic Liquids and Ionic Polymers for the Development of Novel Materials, Processes, and Applications)

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13 pages, 4750 KiB

Open AccessArticle

Novel Chemical Cross-Linked Ionogel Based on Acrylate Terminated Hyperbranched Polymer with Superior Ionic Conductivity for High Performance Lithium-Ion Batteries

by Kang Zhao, Hongzan Song, Xiaoli Duan, Zihao Wang, Jiahang Liu and Xinwu Ba

Polymers 2019, 11(3), 444; https://doi.org/10.3390/polym11030444 - 07 Mar 2019

Cited by 23 | Viewed by 5957

Abstract

A new family of chemical cross-linked ionogel is successfully synthesized by photopolymerization of hyperbranched aliphatic polyester with acrylate terminal groups in an ionic liquid of 1-butyl-3-methylimidazolium tetrafluoroborate (BMIMBF₄). The microstructure, viscoelastic behavior, mechanical property thermal stability, and ionic conductivities of the ionogels are investigated systematically. The ionogels exhibit high mechanical strength (up to 1.6 MPa) and high mechanical stability even at temperatures up to 200 °C. It is found to be thermally stable up to 371.3 °C and electrochemically stable above 4.3 V. The obtained ionogels show superior ionic conductivity over a wide temperature range (from 1.2 × 10⁻³ S cm⁻¹ at 20 °C up to 5.0 × 10⁻² S cm⁻¹ at 120 °C). Moreover, the Li/LiFePO₄ batteries based on ionogel electrolyte with LiBF₄ show a higher specific capacity of 153.1 mAhg⁻¹ and retain 98.1% after 100 cycles, exhibiting very stable charge/discharge behavior with good cycle performance. This work provides a new method for fabrication of novel advanced gel polymer electrolytes for applications in lithium-ion batteries. Full article

(This article belongs to the Special Issue Ionic Systems in Polymer Science: Ionic Liquids and Ionic Polymers for the Development of Novel Materials, Processes, and Applications)

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Review

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31 pages, 12429 KiB

Open AccessReview

Combinations of Antimicrobial Polymers with Nanomaterials and Bioactives to Improve Biocidal Therapies

by Roberto Yañez-Macías, Alexandra Muñoz-Bonilla, Marco A. De Jesús-Tellez, Hortensia Maldonado-Textle, Carlos Guerrero-Sánchez, Ulrich S. Schubert and Ramiro Guerrero-Santos

Polymers 2019, 11(11), 1789; https://doi.org/10.3390/polym11111789 - 01 Nov 2019

Cited by 29 | Viewed by 4589

Abstract

The rise of antibiotic-resistant microorganisms has become a critical issue in recent years and has promoted substantial research efforts directed to the development of more effective antimicrobial therapies utilizing different bactericidal mechanisms to neutralize infectious diseases. Modern approaches employ at least two mixed bioactive agents to enhance bactericidal effects. However, the combinations of drugs may not always show a synergistic effect, and further, could also produce adverse effects or stimulate negative outcomes. Therefore, investigations providing insights into the effective utilization of combinations of biocidal agents are of great interest. Sometimes, combination therapy is needed to avoid resistance development in difficult-to-treat infections or biofilm-associated infections treated with common biocides. Thus, this contribution reviews the literature reports discussing the usage of antimicrobial polymers along with nanomaterials or other inhibitors for the development of more potent biocidal therapies. Full article

(This article belongs to the Special Issue Ionic Systems in Polymer Science: Ionic Liquids and Ionic Polymers for the Development of Novel Materials, Processes, and Applications)

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