The introduction of new ionic moieties, cations and anions, is extending the properties and classical applications of polyelectrolytes. These new polyelectrolytes are being named polymeric ionic ...liquids (PILs) in analogy to their monomeric constituents (i.e. cations such as imidazolium, pyridinium, pyrrolidonium and anions such as hexafluorophosphate, triflates, amidotriflates). This is giving rise to a new family of functional polymers with particular properties and new applications. The first part of this review will focus on the synthetic aspects of PILs and the main aspects related to their physico-chemical properties. In the second part we will review the new technological applications of these polymers such as polymer electrolytes in electrochemical devices, building blocks in materials science, nanocomposites, gas membranes, innovative anion sensitive materials, smart surfaces, and a countless set of applications in different fields such as energy, environment, optoelectronics, analytical chemistry, biotechnology or catalysis.
In the past decade the synthesis of novel stimuli-responsive materials has been driven by the pursuit of new applications and, more recently, sustainable and reusable systems. Of these materials, ...those which incorporate main group Lewis acids (LAs) and bases (LBs) into their polymer backbones have shown extraordinary utility as a result of their synthetic diversity, enabling fine tuning of reactivity and ensuing properties tailored to the desired application. Herein, the recent progress made in the synthesis and applications of macromolecular LAs and LBs is being highlighted. Interactions between polymeric LAs and LBs can be exploited to build supramolecular polymeric networks based on both conventional and frustrated Lewis pairs, while using either functionality individually enables the preparation of sensors for anions, cations, explosives and biological molecules. The presence of polymer-supported LAs/LBs in organocatalysis has been extended to controlling polymer morphology, enabled improvements in activity through compartmentalization and the coexistence of classically incompatible functionalities. Finally, the versatility of this field is being demonstrated by highlighting some of the recent advances in CO2 chemisorption systems employing amine-based polymeric LBs for carbon capture and reduction.
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Synthesis of glycopolymers via click reactions Slavin, Stacy; Burns, James; Haddleton, David M. ...
European polymer journal,
April 2011, 2011-04-00, Volume:
47, Issue:
4
Journal Article
Peer reviewed
Open access
Utilizing sugars with clickable functionalities or polymerizable groups lead to the preparation of tailormade glycopolymers.
This mini-review describes recent work in the field of glycopolymer ...synthesis, with a focus on methods that have employed “click chemistry” and controlled polymerization methodology. A variety of carbohydrates with clickable groups such as azide, alkyne, and thiol moieties provide new routes to glycopolymers. Several studies use copper catalyzed azide-alkyne cycloaddition (CuAAC) reactions to synthesize glycomonomers or to incorporate carbohydrates into a clickable polymeric backbone. Alternatively, there are many thiol based click reactions which provide metal-free synthesis, which are discussed in details.
Aliphatic polycarbonates synthesized from carbon dioxide (CO2) and epoxides are resource‐saving, highly biocompatible and biodegradable polymers. Since the discovery of the copolymerization of ...epoxides and CO2 in 1969 by Inoue et al., this has become an important and useful technology for the large‐scale utilization of CO2 in chemical synthesis, employing mainly propylene oxide, and cyclohexene oxide (CHO). Only in recent years, functionalized polycarbonates have become an emerging topic with a broad scope of potential applications. This review summarizes synthetic routes and properties of numerous functionalized polycarbonates synthesized from CO2 and functional epoxide monomers. Implications for new materials and possible applications, for instance for pharmaceutical purposes and membranes are reviewed. Besides polycarbonates based on oxirane and CHO derivatives, particular emphasis is placed on the manifold synthetic approaches and postpolymerization modifications of glycidyl ether based polycarbonates. Not only functionalized linear polycarbonates are presented but also a variety of novel polycarbonate architectures, e.g., star and hyperbranched polymers.
Functionalized aliphatic polycarbonates based on carbon dioxide (CO2) and tailored epoxide building blocks are a resource‐saving option for a variety of materials and for applications capitalizing on biodegradability and biocompatibility. Besides linear polycarbonates, di and triblock copolymers with polyether and polyester segments as well as other tailored polymer architectures, e.g., amphiphilic and multiarm star polycarbonates, offer great promise as degradable functional materials.
Aggregation‐induced emission (AIE) is a novel photophysical phenomenon coined in 2001 by our group and describes the enhanced light emission of some luminogens in the aggregate or solid state. The ...combination of AIE research and polymer science is a smart approach to produce functional luminescent materials with mechanical strength and excellent processability for real‐world applications. In this feature article, recent progress in AIE polymeric systems, including chemical synthesis and physical blending strategies, is summarized. Through chemical synthesis, various AIE‐active polymers, such as covalently bonded polymers, supramolecular polymers, and nonconjugated luminescent polymers, can be obtained. Serving as environmentally sensitive probes, AIE luminogens can also be physically doped into polymers to generate interesting systems. Finally, outlooks and perspectives on the future direction of AIE polymeric systems are discussed.
Aggregation‐induced emission (AIE) polymeric materials can be prepared through chemical or physical approaches. Various kinds of AIE polymers, such as covalently bonded polymers, supramolecular polymers, and nonconjugated luminescent polymers, can be obtained by chemical synthesis. AIE luminogens can also be physically blended into polymer materials as fluorescent probes, whose emission intensity or wavelength change can reveal the subtle variation of the matrix.
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•Synthesis of sulfur-rich polymers from elemental sulfur-derived polysulfide salts and bisepoxide monomers was reported.•By employing a multifunctional epoxide crosslinker, chemically ...crosslinked polymers with high-sulfur content were fabricated.•Crosslinked polymers were shown to be utilized as adsorbents for mercury removal from water.
The obtainment of polymeric materials out of green, renewable, or sustainable building blocks is an ongoing research area. Due to its large-scale derivation as a by-product of the petroleum industry and natural abundance, elemental sulfur is a prospect to ensure the sustainable production of diverse functional polymeric materials. In the present study a simple yet efficient synthesis of sulfur-rich polymers from elemental sulfur-derived polysulfide salts and bisepoxide monomers was reported. Nucleophilic ring opening step growth polymerization of bisepoxide compounds with bifunctional sulfur derivative sodium pentasulfide (Na2S5) allowed tailorable access to novel linear copolymers with polysulfide chains in the backbone and hydroxyl groups at the side chains. Functional copolymers in the range from 14.8 kDa to 24.5 kDa molecular weights (Mn) were obtained with relatively high monomer conversions (69–91 %). By simple alteration of employed bisepoxide monomers, structurally diverse copolymers were obtained. The polymerizations were efficiently conducted at ambient temperature without the need of any catalyst. Obtained copolymers incorporated alternating hydroxyl functionalities at polymer side chains which were employed as reactive handles for post-polymerization modification. By employing a multifunctional epoxide crosslinker, chemically crosslinked polymers were also fabricated. These crosslinked polymers were shown to be utilized as adsorbents for mercury removal from water. The obtained results in this study demonstrated that the proposed methodology can be employed to synthesize and fabricate structurally diverse sulfur-rich polymers that might find potential use in various material applications.
It has been almost two decades since the concept of ‘click’ chemistry was anchored in the monumental field of chemistry. Later, numerous chemical approaches have been implemented that exhibit ...features kindred to ‘click’ chemistry toolbox. Unlike the synthesis of organic compounds involving typical purification procedures, the modular and orthogonal ‘click’ concept substantially embraces the material research community with delineating innumerable macromolecular architectures. In polymer chemistry, there are various types of ‘click’ reactions like copper (I) catalyzed alkyne-azide (CuAAC), strain promoted alkyne-azide cycloaddition (SPAAC), Diels-Alder, Alder-ene, thiol-ene, thio-bromo, etc., are used to prepare different functional polymers. Among the various ‘click’ reactions, recently, the ultrafast ‘click’ modification based on different 1,2,4-triazoline-3,5-dione (TAD) derivatives has gained tremendous attention in the broad platform of polymer research. Similar to singlet oxygen, the heterocyclic TAD reagents undergo ‘click’ conjugation within a concise timescale. Following the uncovering of the conventional routes for synthesizing TADs, few spellbinding categories of research have been carried out to develop different functional polymers for diverse applications. The perspective of this review is to cover the recent fascinating outcomes from TAD based ultrafast ‘click’ modification of macromolecules. This review highlights the present state-of-the-art of synthesis of new TAD molecules and their use in designing different macromolecular systems with remarkable features based on ultrafast TAD ‘click’ chemistry.
Macromolecular engineering using TAD chemistry, shown via a sketch of a fictional character Mr. Bean, a distinguished comedian, and engineer, with his TAD toolbag. Display omitted
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•Caffeic acid is successfully grafted onto PLA-b-PHEMA polymer.•Grafted copolymer exhibits antimicrobial and antioxidant properties.•Films are prepared by combining commercial PLA ...with different proportions of PLA-b-PHEMA-g-CA using a solvent casting method.•Functional films display antioxidant and antimicrobial attributes.
Derived from renewable sources like corn starch or sugarcane, poly(lactic acid) (PLA) presents an eco-friendly alternative to traditional petroleum-based plastics. PLA lacks inherent functional groups, posing a challenge for certain applications. The modification and functionalization of PLA contribute to the facilitation of innovative applications across diverse fields. To address this limitation, in this study a bioactive compound, caffeic acid, strategically grafted the onto poly(D,L-lactide)-b-poly(2-hydroxyethyl methacrylate) block copolymer (PLA-b-PHEMA). The resulting caffeic acid grafted copolymer (PLA-b-PHEMA-g-CA) was characterized by size exclusion chromatography, NMR, UV–Vis and FT-IR spectroscopies, and then blended with commercial PLA to produce films. The synthesis involves polymerizing 2-hydroxyethyl methacrylate with a poly(D,L-lactide) macroinitiator via ATRP method, yielding PLA-b-PHEMA. Subsequent functionalization via Steglich esterification yields PLA-b-PHEMA-g-CA. Characterization indicated a grafting ratio of 60.7%. Both grafted copolymer and films exhibited antioxidant property and antimicrobial effect against S. aureus and E. coli, showcasing potential applications in sustainable materials.
We report new efficient and cost-effective polymeric bifunctional materials those were evaluated as Cu2+ ions adsorbents and for antimicrobial properties. Two crosslinked polymers were synthesized by ...thermal polymerization and in situ crosslinking of acrylic acid (AAc) with ethyleneglycol dimethacrylate (EGDMA) or divinylbenzene (DVB) using ammonium persulphate (APS) as initiator. Poly(acrylic acid) PAAc was functionalized to improve its efficiency and selectivity in the targeted applications alongwith antimicrobial properties by incorporating thiosemicarbazide (TS) on the –COOH groups. The synthesized three-dimensional crosslinked PAAc–cl–EGDMA and PAAc–cl–DVB were converted to their corresponding esters (–COOCH3) by reflux method and further modified with TS to obtain PATS–cl–EGDMA and PATS–cl–DVB, where ATS stands for thiosemicarbazide acrylate. The synthesized networks were characterized using AFM, SEM, 13C NMR, FTIR, XRD, and EDX studies to evaluate their structure. The presence of TS moieties imparted bifunctional characteristic to the polymers with effective and selective Cu2+ ions adsorption and antimicrobial properties.
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•Two new crosslinked polymeric networks, with different crosslinker, were synthesized.•Simple green protocols were followed in synthesis.•These were further functionalized with thiosemicarbazide to induce bifunctional properties.•Evaluated as rapid, highly selective, efficient and reusable Cu2+ ions adsorbents.•These possess appreciable antimicrobial properties.
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This comprehensive review surveys recent research trends in the addition polymerization of functionalized norbornenes for the macromolecular design of high performance materials in ...terms of catalyst activity, monomer reactivity, modifications and potential applications of addition polynorbornenes bearing functional groups. The structure of addition polynorbornene backbones is responsible for their high thermal resistance and chemical stability. In order to impart desired properties to the polymers, various functional side groups can be incorporated into the monomer units by the Ti-, Ni-, or Pd-catalyzed polymerization of norbornenes, which are available via cycloaddition reactions or norbornadiene-2,5 modifications. Based on the use of different substituents in the norbornene monomer units and different polymer compositions, the addition polynorbornenes have been successfully developed for the preparation of pervaporation, gas-separation, and proton-conducting membranes, sensors, catalyst supports, and for applications as photoresist, electrooptical, and dielectric materials etc.
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