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  • Beyond PEO—Alternative Host Materials for Li+-Conducting Solid Polymer Electrolytes
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2018-01-03
    Jonas Mindemark, Matthew J. Lacey, Tim Bowden, Daniel Brandell

    The bulk of the scientific literature on Li-conducting solid (solvent-free) polymer electrolytes (SPEs) for applications such as Li-based batteries is focused on polyether-based materials, not least the archetypal poly(ethylene oxide) (PEO). A significant number of alternative polymer hosts have, however, been explored over the years, encompassing materials such as polycarbonates, polyesters, polynitriles, polyalcohols and polyamines. These display fundamentally different properties to those of polyethers, and might therefore be able to resolve the key issues restricting SPEs from realizing their full potential, for example in terms of ionic conductivity, chemical or electrochemical stability and temperature sensitivity. It is further interesting that many of these polymer materials complex Li ions less strongly than PEO and facilitating ion transport through different mechanisms than polyethers, which is likely critical for true advancement in the area. In this review, 30 years of research on these ‘alternative’ Li-ion-conducting SPE host materials are summarized and discussed in the perspective of their potential application in electrochemical devices, with a clear focus on Li batteries. Key challenges and strategies forward and beyond the current PEO-based paradigm are highlighted.

  • From nano to micro to macro: Electrospun hierarchically structured polymeric fibers for biomedical applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-12-30
    Guang Yang, Xilin Li, Yang He, Junkai Ma, Guoli Ni, Shaobing Zhou

    Hierarchically structured polymer fibers encompassing 1-D, 2-D, and 3-D structures with at least one dimension nano- to micro-meters in size have recently received an increasing amount of attention due to their vast potential in such applications as sensing, medicine, energy storage. This review summarizes advancements in the last ten years in the design and fabrication of hierarchically structured polymer fibers via electrospinning technologies, including a diversity of electrospinning devices and electrospinning parameters using various polymers. These well-defined, multilevel structures enable the fibers to be used more effectively in applications in the biomedical field, such as drug delivery, tissue engineering, and diagnostics. This review can provide a better understanding of the relationships between the structure and functionality of polymer fibers for further biomedical applications.

  • Manipulation of interactions at membrane interfaces for energy and environmental applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-12-21
    Jing Zhao, Guangwei He, Guanhua Liu, Fusheng Pan, Hong Wu, Wanqin Jin, Zhongyi Jiang

    Synthetic membranes play an increasingly critical role in various energy and environment-related applications such as carbon capture and water purification. Owing to the great promise in solving the permeability/selectivity trade-off and the separation performance/stability trade-off, heterogeneous membranes primarily including mixed matrix membranes and composite membranes have become a prevalent membrane configuration in various membrane processes. For heterogeneous membranes, interfacial interaction is an essential factor, which governs the nano-/molecular-scale assembly of membrane materials, tunes the hierarchical structures and enhances the comprehensive properties of membranes. This review highlights the recent advances in manipulating interfacial interactions of heterogeneous membranes with the focus on two kinds of typical interfaces: the separation layer-support layer interface in composite membranes and the polymer matrix-filler interface in mixed matrix membranes. Common methods for interfacial interactions manipulation of heterogeneous membranes are extensively summarized. The applications of manipulating interactions at membrane interfaces in energy and environment-related realms are briefly introduced. Finally, the future directions of manipulating interfacial interactions of heterogeneous membranes are tentatively identified.

  • Protein-mimetic peptide nanofibers: motif design, self-assembly synthesis, and sequence-specific biomedical applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-12-16
    Wensi Zhang, Xiaoqing Yu, Yang Li, Zhiqiang Su, Klaus D. Jandt, Gang Wei

    The design and fabrication of self-assembled peptide nanostructures offer an amazing platform for creating functional nanomaterials for various biomedical applications. Utilizing the mechanical and biological advantages of the protein-mimetic peptide (PMP) system, and combining self-assembled PMP nanofibers with other nanomaterials like nanoparticles, the fabricated PMP-based hybrid fibrous nanostructures can serve as promising candidates for advanced technological applications. In this review, we present the design, synthesis, modification, and fabrication of PMP nanofibers by mimicking the properties and functions of several types of proteins, including extracellular matrix proteins, silk proteins, amyloid proteins, and heparin. The sequence and motif design of PMPs, and the relationships between the design of PMP monomers and the fabrication of functional fibrous biomaterials are introduced and discussed. Furthermore, we summarize a basic classification of various peptide motifs, and provide some instructions for the function-based design of peptide nanostructures, in which some issues on the motif design and function tailoring are discussed. Finally, the recent advances in the PMP nanofiber-based functional nanomaterials in biomineralization, cell culture, tissue regeneration, drug delivery, hemostasis, bioimaging, and biosensors are presented in detail. We believe that this review will be very helpful for researchers to understand the property-specific molecular design, controllable supramolecular self-assembly, and motif-specific applications of both peptides and proteins.

  • A comprehensive review on polymer single crystals-From fundamental concepts to applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-11-26
    Samira Agbolaghi, Saleheh Abbaspoor, Farhang Abbasi

    Polymer single crystals and correlated crystalline structures are reviewed by emphasizing the last 10-20 years of research on fundamental concepts, single crystal engineering, and applications. The review commences with basic work comprising morphologies, theories, and especial single crystals, subsequently passes to star block, brush-covered, well-oriented, patterned, epitaxial, non-flat and degradable single crystals, and eventually reviews single crystals and nano-particles/structures including magnetically recyclable catalyst supports, nano-hybrid shish-kebabs to mimic the natural bone nanostructures, and nano/micromotors. Other applications are also presented and discussed in detail, including exploiting conductive single crystals of poly(3-hexylthiophene-2,5-diyl) and poly(3,4-ethylenedioxythiophene) in field-effect transistors, nanowires and microwires, as well as fostering amino-functionalized lamellar poly(L-lactide) single crystals as a delivery system for human papillomaviruses-associated tumors.

  • Porous ionic polymers: Design, synthesis, and applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-11-23
    Dan Xu, Jiangna Guo, Feng Yan

    Porous ionic polymers (PiPs) are newly emerging organic porous polymers. In sharp contrast to charge-neutral porous polymers, ionic moieties are either incorporated into the polymer backbone, or are covalently attached to a polymeric framework. Therefore, their physicochemical properties, functional groups, and active sites can be easily modified through screening of building blocks and ionic tectons. Meanwhile, their surface area, pore size, and pore volume can also be tuned by counterions exchange. Intrinsic functionalization further broadens the application range of the PiPs. This review will describe the recent advancements with regard to PiPs, and their development in the area of gas adsorption, catalysis, antibacterial applications and water purification.

  • Poly(disubstituted acetylene)s: Advances in Polymer Preparation and Materials Application
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-11-21
    Xiao Wang, Jing Zhi Sun, Ben Zhong Tang

    Conjugated polymers (CPs) have drawn great attention due to their excellent optical and electronic properties for decades. Among the varieties of CPs, polyacetylenes (PAs) triggered a revolution in polymer science due to their conductivity in highly doped state. Yet, the unstability and unprocessability of the pristine polyacetylene led researchers exploring their derivatives with substituents. Luckily, greatly improved stability and processability have been achieved by poly(disubstituted polyacetylene)s or PDSAs, that show efficient fluorescence emission in both solution and solid state and excellent circular polarized luminescence. This review summarizes recent research regarding PDSAs, beginning with the novel achievements of the discovery of the Pd-based catalyst systems for the polymerization of disubstituted acetylene monomers (DSAms), followed by a description of the effect of polymerization catalysts on the stereochemistry of obtained polymers and the effect of the stereochemistry on functional properties. Then, an updated summary of alternative synthetic routes to PDSAs, that is, post-polymerization modifications is contributed. This strategy has shown strong vitality due to the highly efficient reaction tools furnished by organic chemists such as click chemistry and activated esters. PDSAs usually possess intrinsically porous structure, exhibiting significant and variable fluorescent responses to exotic species such as solvents with different polarities, metal cations and explosives, and these properties indicate that PDSAs are promising candidates for fluorescent sensors and probes. Their reversible responses to applied fields such as stress and fluid gradient allow PDSAs to be active components of actuators. Moreover, due to the unique conjugated polyene main-chain and metathesis polymerization mechanism, PDSAs pronounced chirality transfer capacity and outstanding circular polarized luminescent property. Finally, an outlook of the application and suggestions of the synthetic efforts are forwarded.

  • Preparation, microstructure, and microstructure-properties relationship of thermoplastic vulcanizates (TPVs): A review
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-11-20
    Nanying Ning, Shangqing Li, Hanguang Wu, Hongchi Tian, Pengjun Yao, Guo-Hua Hu, Ming Tian, Liqun Zhang

    It is common practice to blend polymers to obtain high-performance polymer materials for new applications. Thermoplastic vulcanizates (TPVs), consisting of a high content of crosslinked rubber as a dispersed phase and a low content of thermoplastic as a continuous phase, are usually prepared by pre-blending rubber and plastic phases followed by dynamic vulcanization. They are a special class of high performance thermoplastic elastomers (TPEs) as they combine both the excellent elasticity and mechanical properties of crosslinked rubbers and good processability and recyclability of thermoplastics. As such, in the recent decades they have attracted much attention and have become the fastest growing elastomers to replace unrecyclable thermoset rubbers. This review focuses on recent progresses in TPVs, and more specifically on the following issues: (1) preparation methods of TPVs, (2) mechanisms of formation of the microstructure of TPVs; (3) relationships between the microstructure and properties, (4) review of various types of TPVs, including general TPVs, special TPVs, bio-based TPVs, and TPVs-based nanocomposites, (5) future challenges on TPVs.

  • Radical polymerization of acrylic monomers: An overview
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-11-14
    Nicholas Ballard, Jose M. Asua

    Since their discovery and development in the 20th century, acrylic polymers have become an integral part of numerous industries and are used in a myriad of applications. As is true for many polymers, the suitability of a particular polyacrylate for a given application comes from its structure, which is determined during its synthesis in the reactor, long before commercial use. Uniquely, the radical polymerization of acrylic monomers is strongly affected by radical transfer events which dictate reaction kinetics and lead to a range of distinct macromolecular structures, a fact that went unknown for many years and continues to generate unexpected results. In this review, we aim to present the current picture of the various competitive processes which occur during polymerization of acrylic monomers, as well as the ongoing issues that hinder our complete comprehension of this complicated monomer family.

  • Let spiropyran help polymers feel force!
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-11-08
    Meng Li, Qi Zhang, Yin-Ning Zhou, Shiping Zhu

    Mechanoresponsive polymers have garnered significant attention in recent years, due to their great potential application in stress/strain sensing and damage warning. Several reviews of mechanochemistry have been published recently. In this review, we mainly focus on the most established mechanophore, spiropyran (SP), from an engineering perspective. We present a workflow for SP mechanochemistry, applications in various polymeric systems and impacting factors, as well as characterization techniques. Current limitations and future research directions are briefly highlighted in the end. This review aims to offer deep insight into polymer mechanochemistry and provide approaches to study other mechanophores using the example of SP mechanochemistry in polymers.

  • Molecular self-assembly of one-dimensional polymer nanostructures in nanopores of anodic alumina oxide templates
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-11-01
    Hui Wu, Yuji Higaki, Atsushi Takahara

    One-dimensional (1-D) polymer nanostructures have attracted much attention due to their unique properties and many potential applications in areas such as sensors, transistors, separation, storage, and photovoltaic cells. This is a review of research activities on 1-D polymer nanostructures fabricated by anodic aluminum oxide (AAO) templates. The preparation methods of polymer nanostructures by AAO templates including polymer melt infiltration, polymer solution infiltration, and chemical synthesis are introduced. According to the molecular structure of polymers, the morphology, and properties of seven types of polymers, amorphous homopolymers, amorphous-amorphous block copolymers, amorphous/amorphous polymer blends, semicrystalline homopolymers, semicrystalline/amorphous polymer blends, semicrystalline-amorphous block copolymers, and semicrystalline-semicrystalline block copolymers in nanopores are demonstrated.

  • Progress in electrospun polymeric nanofibrous membranes for water treatment: fabrication, modification and applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-10-26
    Yuan Liao, Chun-Heng Loh, Miao Tian, Rong Wang, Anthony G. Fane

    Research on membrane technologies has grown exponentially to treat wastewater, recycle polluted water and provide more freshwater. Electrospun nanofibrous membranes (ENMs) exhibit great potential to be applied in membrane processes due to their distinctive features such as high porosity of up to 90% and large specific surface area. Compared with other nanofiber fabrication techniques, electrospinning is capable of developing unique architectures of nanofibrous scaffolds by designing special assemblies, and it is facile in functionalizing nanofibers by incorporating multi-functional materials. This review summarizes the state-of-the-art progress on fabrication and modification of electrospun polymeric membranes with a particular emphasis on their advances, challenges and future improvement in water treatment applications. First, we briefly describe the complex process governing electrospinning, illustrate the effects of intrinsic properties of polymer solutions, operational parameters and surrounding environment conditions on the formation of nanofibers and resultant nanofibrous membranes, and summarize various designs of electrospinning apparatus. That is followed by reviewing the methods to prepare multifunctional composite ENMs, assorted into three categories, including modification in nanofibers, loading target molecules onto nanofibers surface, and implementing selective layers on the ENM surface. Comprehensive discussion about past achievements and current challenges regarding utilization of composite ENMs in water treatment are then provided. Finally, conclusions and perspective are stated according to reviewed progress to date.

  • Silicon-Containing Block Copolymers for Lithographic Applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-10-16
    Ting-Ya Lo, Mohan Raj Krishnan, Kai-Yuan Lu, Rong-Ming Ho

    This comprehensive review, summarizes recent advances in the fabrication of well-ordered block copolymer (BCP) thin films by different methods, focusing on the development of silicon-containing BCPs as candidates for lithographic applications. With the advantage of Si-containing blocks, these BCPs offer much smaller feature sizes due to large segregation strength and high etch contrast for the fabrication of well-defined nanopatterns with high resolution. Considering that poly(dimethylsiloxane) (PDMS)-containing BCPs are widely studied systems among Si-containing BCPs, the possibility of using PDMS-containing BCPs for lithographic applications is demonstrated through previous and ongoing key research.BCP lithography will lead to the development of next-generation microelectronic devices by providing a simple and scalable nanopatterning method for the fabrication of microelectronic devices in which the feature sizes and geometries are controlled by tuning the chain lengths and volume fractions of the block copolymers. The control of microdomain orientation and alignment in thin film BCPs is crucial for lithographic applications. The principles and limitations of various methods to orientation are discussed, including temperature-gradient, surface modifications, solvent annealing/evaporation and other new types of annealing process.Directed self-assembly (DSA) of BCP on topographic or chemically patterned substrates has attracted a great attention from academic and industrial research since it offers the advantage of defect free nanopatterning at large scales. The key achievements in DSA methods are elaborated in the subsequent parts of this review. New trends for lithographic applications and the applications beyond lithography using Si-containing BCPs for nanopatterning are also discussed, and finally, concluding remarks and perspectives for BCP lithography are presented.

  • A review on enzymatic polymerization to produce polycondensation polymers: The case of aliphatic polyesters, polyamides and polyesteramides
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-10-06
    Aliki Douka, Stamatina Vouyiouka, Lefki-Maria Papaspyridi, Constantine D. Papaspyrides

    Enzymatic polymerization represents today an effective and preferable alternative to conventional chemically-catalyzed processes. It offers significant advantages, summarized in the applied mild reaction conditions mainly in terms of temperature and toxicity, and high selectivity of enzymes, avoiding protection-deprotection strategies and resulting in improved quality/performance of end products. Especially for polycondensation polymers, biocatalyzed synthetic routes have been under research for the last thirty years, including homo- and copolymerization of a significant number of monomers. Aliphatic polyesters, polyamides and at a much lower extent polyesteramides, represent the core of the pertinent studies, and are systematically discussed in the current review. Emphasis is given on polycondensates with biodegradability properties, derived from bio-based monomers such as succinic acid, 1,3- propanediol and lactide/lactic acid.Free or immobilized lipases and cutinases are the predominant biocatalysts in the relevant polymer families, being used in polycondensation as well as in ring-opening reaction schemes. The efficiency of the different biocatalytic processes is herein correlated to important process parameters, such as the enzyme and monomer type, the reaction temperature and time, the polymerization technique (solution or solvent-free), as well as the by-product removal method, e.g., application of vacuum, water absorption by molecular sieves, azeotropic distillation.

  • Free-radical polymerizations of and in deep eutectic solvents: green synthesis of functional materials
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-10-05
    Josué D. Mota Morales, Regina J. Sánchez-Leija, Arturo Carranza, John A. Pojman, Francisco del Monte, Gabriel Luna-Bárcenas

    The increasing environmental awareness has led to the search for alternative reaction media to reduce or eliminate the use of organic solvents in polymer science. Deep eutectic solvents (DESs), a subclass of ionic liquids, have emerged as sustainable solvents for a plethora of chemical reactions. In this Trend Article, DES utilization in free-radical polymerizations will be discussed. Two main fields of application are reported. In the first section, monomers able to undergo free-radical polymerization while taking part in a DES, as hydrogen bond donor or ammonium salt, so called DES monomers, are presented. In the second section, the role of DES as solvents, where the polymerization takes place, either in the same phase or in an emulsion, is described. Finally, the properties of the polymers resulting from these particular methods of synthesis are discussed with emphasis on their green aspects.

  • Polymerizations based on triple-bond building blocks
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-09-29
    Yong Liu, Anjun Qin, Ben Zhong Tang

    Development of new polymerizations based on triple-bond building blocks has received considerable research attention, from which polymers with unique structures and advanced functions can be generated. In this review, we summarize the research efforts on using alkynes and nitrogen-containing triple bonds as building blocks to prepare polymers with linear and topological structures since 2010. The metathesis polymerization and polyaddition of mono- and di-substituted acetylenes, the Cu(I)-catalyzed and metal-free azide-alkyne click polymerization, the thiol-yne click polymerization, polycyclotrimerization of diynes, and the polymerizations based on cyanide and isocyanide monomers are discussed in detail. Moreover, the unique stoichiometric imbalanced polymerization based on alkynes is also briefly introduced. The functions and applications of polymers, produced from these developed polymerization reactions, such as aggregation-induced emission, self-healing, fluorescent patterning, liquid crystal, fluorescence sensing, explosive detection, chiral catalysis and gas permeability are also reviewed.

  • Versatile types of hydroxyl-rich polycationic systems via O-heterocyclic ring-opening reactions: from strategic design to nucleic acid delivery applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-09-20
    Fu-Jian Xu

    Safe and effective vectors play an important role in nucleic acid delivery processes. Ring-opening reactions are quite often used to produce biomaterials with various functions and properties. Instead of surface-conjugated hydrophilic polymers such as polyethylene glycol, uniformly-distributed hydroxyl groups within one polycation could improve biocompatibility and benefit nucleic acid delivery performances. Hydroxyl groups with uniform distribution are readily produced by ring-opening of O-heterocyclic units. O-Heterocyclic units include cyclic ester (epoxide), carbonate and lactones. Hydroxyl-rich polycationic systems are prepared predominately with aminated poly(glycidyl methacrylate) (PGMA). PGMA is the most common epoxy polymer and can be post-modified readily via epoxide ring-opening reactions by different amine species. Hydroxyl-rich polycationic systems are also reported by ring-opening polymerization between various epoxy and amine units. In addition, post hydroxylation of polycations via different O-heterocyclic ring-opening reactions could give rise to various hydroxyl-rich polycationic systems. More recently, versatile types of hydroxyl-rich polycationic systems with special molecular and topological structures, such as linear, star-shaped, comb-shaped, supramolecular, branched, hierarchical, and hetero-nanostructured carriers, are well studied. This review summarizes recent research activities in hydroxyl-rich polycationic systems. Their different design strategies via O-heterocyclic ring-opening reactions and unique nucleic acid delivery applications are described in detail. The research activities indicate that hydroxyl-rich polycationic systems become versatile and powerful candidates for the development of advanced multifunctional delivery systems of nucleic acids.

  • Catechol functionalized hyperbranched polymers as biomedical materials
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-09-12
    Hong Zhang, Tianyu Zhao, Ben Newland, Wenguang Liu, Wei Wang, Wenxin Wang

    The catechol plays a variety of important roles in biological processes, prompting researchers to include them in the design of biomimetic biomedical materials. The low molecular weight and good water solubility of the catechol group (or its derivatives) make it a good candidate for functionalizing biomaterials that can be typically achieved by grafting it onto a polymer chain. To fully harness the powerful capabilities of catechols, one can think beyond grafting to linear polymer chains, towards hyperbranched polymers, wherein at least one of the branches comprises at least one catechol moiety. In recent years, a number of approaches have been developed to synthesize multifunctional hyperbranched polymers with catechol functionalities for bioadhesives and surface coatings. This review article focuses on the main synthetic approaches applied for introducing the important and versatile catechol building blocks within the (hyper)branched structure polymers. In addition, the applications of these polymers in biomedical fields are highlighted as well.

  • Polymer composite hydrogels containing carbon nanomaterials—Morphology and mechanical and functional performance
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-09-08
    Ashraful Alam, Yongjun Zhang, Hsu-Chiang Kuan, Sang-Heon Lee, Jun Ma

    Carbon nanomaterials have been the centre of intensive research because of their unique structure and technologically useful properties. We herein review the effect of the nanomaterials on the morphology and mechanical and functional properties of composite hydrogels, by critically examining the nanomaterial dispersion in aqueous media and their interaction with polymer matrices. We focus on synthesis methods and the mechanical, electrical and swelling properties of the hydrogels with emphasis on cross-linking techniques and structure-property relations. The nanomaterial properties and fabrication techniques are briefly discussed highlighting advantages and limitations. This review outlines the current challenges and opportunities to effectively utilizing carbon nanomaterials for polymer hydrogels. The output of such materials would be valuable to soft materials scientists and composite engineers, as well as those working on water-soluble, synthetic polymers.

  • Electrospun Nanofiber: Emerging Reinforcing Filler in Polymer Matrix Composite Materials
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-08-08
    Guolong Wang, Demei Yu, Ajit D. Kelkar, Lifeng Zhang

    The rapidly developing technique of electrospinning has gained surging research interest since the 1990s due to its capability of yielding continuous fibers with diameters down to the nanometer scale. Despite enormous efforts devoted to explore applications of electrospun nanofibers, such as separation, catalysis, nanoelectronics, sensors, energy conversion/storage, and biomedical utilization, there are limited attempts to employ these nanofibers for reinforcement in polymer composites. Electrospun nanofibers, however, possess comprehensive advantages not typically shared by other nanoscale composite fillers/reinforcing agents, such as continuity, diverse material choice, controlled diameter/structure, possible alignment/assembly, mass production capability and so forth. Therefore electrospun nanofibers have great potential as promising reinforcement fillers for next-generation polymer composites. This is a comprehensive and state-of-the-art review of the latest advances made in development of electrospun nanofiber reinforced polymer composite materials with intention to stimulate interests in both academia and industry.

  • Graft Modification of Natural Polysaccharides via Reversible Deactivation Radical Polymerization
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-08-04
    Omar Garcia-Valdez, Pascale Champagne, Michael F. Cunningham

    Interest in the development of new hybrid materials based on natural polysaccharides has grown exponentially in the last decade. Such materials are commonly obtained by the graft modification of polysaccharides via reversible deactivation radical polymerization (RDRP). Research has focused on the use of RDRP techniques, including ATRP (atom transfer radical polymerization), NMP (nitroxide-mediated polymerization) and RAFT (reversible addition–fragmentation chain transfer polymerization), not only because of the good control over the molecular weight distribution that RDRP provides, but also because of the complex macromolecular architectures that can be achieved. This review highlights the most recent development, challenges, uses and applications of the polymer graft modification of several common natural polysaccharides (chitin, chitosan, alginate, dextran, starch and cellulose derivatives) via RDRP.

  • Old meets new: Combination of PLA and RDRP to obtain sophisticated macromolecular architectures
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-08-02
    Ilknur Yildirim, Christine Weber, Ulrich S. Schubert

    This review article highlights the research focused on the synthesis of polylactide (PLA) based copolymers by combination of reversible-deactivation radical polymerization (RDRP) techniques with ring-opening polymerization (ROP) processes. In particular atom-transfer radical polymerization (ATRP), reversible addition-fragmentation chain transfer (RAFT) polymerization, and nitroxide-mediated polymerization (NMP) will be addressed as polymerization (RDRP) techniques mechanistically different from ROP in the design of various sophisticated macromolecular structures. The combination of ROP with RDRP techniques has been extensively applied to prepare PLA copolymers. We discuss the synthetic methods applicable to prepare linear and star-shaped block copolymers by use of heterofunctional initiators as well as other end functionalization methods. This is complemented with the adaption of the synthetic pathways generally used for the preparation of comb and graft copolymers, i.e., macromonomer, grafting-from and grafting-onto approaches, to the requirements of PLA-based building blocks.

  • Synthesis of hybrid materials using graft copolymerization on non-cellulosic polysaccharides via homogenous ATRP
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-08-02
    Farzad Seidi, Hamid Salimi, Ahmad Arabi Shamsabadi, Meisam Shabanian

    Inclusion of various polymeric chains with different lengths and functionalities (such as hydrophobic, ionic, acidic, basic, etc) into polysaccharide backbones leads to new polymeric materials with interesting properties that may self-assembled into different aggregations and have the potential to for use in a variety of applications. This review highlights the application of various ATRP techniques (such as “grafting-from” and “grafting-to”) to modify non-cellulosic polysaccharides under homogenous condition. Chemical modification of chitosan, pullulan, dextran, agarose, hyaluronic acid (hyaluronan), starch, glycogen, heparin, chitin, guar gum, locust bean gum, and dextrin using ATRP are described. Pre-functionalization or protection of some functional groups in the polysaccharide backbone required in some cases to prepare a precursor with higher solubility in organic solvents is illustrated. For each polymerization, the strategy for synthesis of the copolymer and the condition of the polymerization is described in detail along with the properties of the prepared copolymers. Furthermore, examples that produced materials with the potential for use in a specific application are reviewed in summary.

  • Chemical Synthesis of Polysaccharides and Polysaccharide Mimetics
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-08-01
    Ruiqing Xiao, Mark W. Grinstaff

    Polysaccharides are ubiquitous in nature, and play many critical roles in biology. As such, the synthesis of polysaccharides and polymers mimicking the structure or function of polysaccharides is of keen interest in order to reveal structure-function relationships and to prepare biocompatible and biodegradable materials for research and commercial applications. Recent developments in polymerization methodologies are enabling the synthesis of polysaccharides and polysaccharide mimetics with a variety of structures and architectures. While there have been significant advances in overcoming the difficulties in controlling the regioselectivity and stereospecificity of glycosidic bond formation during polymerization, the development of efficient synthetic routes with general applicability to stereoregular and structurally complex polysaccharides remains a challenge. This review comprehensively describes the chemical polymerization methods to synthesize polysaccharides with different compositions and architectures (linear, branched, and hyperbranched) and the synthetic procedures to polysaccharide mimetics possessing, for example, amine linkages, amide linkages, and carbonate linkages. It begins with a discussion of the challenges and strategies for the synthesis of polysaccharides. We highlight the complexity observed in theses macromolecules due to the number and variety of stereo- and regio-types of glycosidic linkages present between monosaccharide residues. With regards to polysaccharide mimetics, we focus on polymers displaying important structural features present in natural polysaccharides, such as a rigid polymer backbone containing heterocyclic ring structures, short linkages with less than three atoms, as well as multiple hydroxyl groups. Both condensation polymerization and ring-opening polymerization are used to prepare linear polysaccharides, branched polysaccharides, hyperbranched polysaccharides, non-O-glycosidic linked polysaccharide mimetics, and pseudopolysaccharides. The review concludes with reflections and suggestions for future directions of investigation.

    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-28
    Chunliang Lu, Marek Urban

    Polymeric nanomaterials capable of altering volume, color, or shape have attracted significant scientific interests as these materialsbecome increasingly critical in advancing uniquetechnological developments. Design, synthesis, and assembly of nanomaterials with precisely controlled shapes and directional responsivenessare particularly criticalin the development of new functional, near-device level materials. Spatial anisotropies are typically introduced by the placement of symmetrically orasymmetricallylocated responsive components enabling either interactions with the environment manifested by dimensional or color changes, energy storage and transfer, or diffusion. This review outlines recent advances in the synthesis, fabrication, and assemblyofisotropic and anisotropic polymer-based nanomaterials in whichdimensional, color, and morphologicalchanges are induced by external stimuli. Specifically, core-shell, hollow, Janus, gibbous/inverse gibbous nanoparticles prepared with precisely controlled morphologies capable of spatially responding totemperature, pH, electromagnetic radiation or biological changes are discussed. Recent advances in the nanoparticle surface modifications which are introduced to guide nanomaterialsto selectively interact and communicate with the environment are also highlighted.Since high aspect ratio nanomaterials, including polymeric nanowires or nanotubes containing responsive components, are particularly attractivein the development of 3D multi-functional objects, their manufacturingas well as applications are examined.Although many uses of stimuli-responsive nanomaterials in electronics, energy conversion, sensing, or biomedicine and other technologies are already in place, there are limitless opportunities for new applications as long as proper regulatory measures are exercised to elevate the impact of these materials on the environment. Polymeric stimuli-responsive nanomaterials offer a tremendous opportunity for the development of cognitive materials’ systems, particularly when protein-like polymers containing amino acids joined by polypeptide bonds with enzymes or sugar-phosphate moieties as well as other sugar-containinginteractions are utilized as building blocks and components of future materials.

  • Degradable thermosets based on labile bonds or linkages: a review
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-25
    Songqi Ma, Dean C. Webster

    Compared with thermoplastic polymers, thermoset polymers are difficult to recycle because they can not be remolded once cured and often do not decompose under mild conditions. Thermosets designed to be degradable afford a useful route to obtain thermoset recyclability and enable the recycling of valuable components that may be encapsulated in thermoset materials. In this review, the need for degradable thermosets as well as a summary of research progress is presented. Degradable thermosets are divided into different categories based on the different labile bonds or linkages studied such as esters, sulfur containing linkages (disulfide, sulfonate, 5-membered cyclic dithiocarbonate, trithiocarbonate, sulfite), nitrogen containing structures (acylhydrazone, alkoxyamine, azlactones, Schiff base, hindered ureas, aminal, carbamate), orthoester structures, carbonates, acetals, hemiacetals, olefinic bonds, D-A addition structures, vicinal tricarbonyl structures, peroxide bonds, phosphorus containing structures, tertiary ether bonds, and so on. The synthetic route, recycling methods, degradation mechanisms and progress in research of each approach to degradable thermosets is described. The efforts of the applicability of some degradable thermosets are also summarized. Finally, conclusions and trends of future work are highlighted.

  • Antimicrobial Polymeric Nanoparticles
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-21
    Shu J. Lam, Edgar H.H. Wong, Cyrille Boyer, Greg G. Qiao

    Currently, infections caused by multidrug-resistant bacteria have reached critical levels. Thus, various approaches are being explored for the development of new and effective antimicrobial agents, one of which lies in the form of polymeric nanoparticles. Driven by the significant advancements in controlled polymerization techniques over the last few decades, antimicrobial polymeric nanoparticles have recently been investigated as potential new antibiotics to combat the rise of infectious diseases. This review aims at presenting an overview of the history and state-of-the-art of antimicrobial polymeric nanoparticles including their available structure-activity relationship, and highlights the impact of controlled polymerization has on the antimicrobial field as well as some of the key challenges that still need to be overcome for potential clinical applications. Herein, potential new developments are suggested as well.

  • Water-insoluble β-cyclodextrin–epichlorohydrin polymers for removal of pollutants from aqueous solutions by sorption processes using batch studies: A review of inclusion mechanisms ☆
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-20
    Nadia Morin-Crini, Peter Winterton, Sophie Fourmentin, Lee D. Wilson, Éva Fenyvesi, Grégorio Crini

    Although water-insoluble cyclodextrin-epichlorohydrin polymers have been known for half a century, these materials are of continued interest to the scientific community, in particular for their interesting environmental applications as sorbents in liquid-solid sorption processes. However, in spite of the abundance of literature and conclusive results obtained at the laboratory scale, interpreting the mechanisms of pollutant elimination remains an interesting source of debate and sometimes of contradiction. This review summarizes and discusses the various mechanisms proposed in the literature. A distinction was made in the description of these interactions depending on whether the polymer structures were modified or not.

  • Shear thickening fluids in protective applications: A review
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-18
    Selim Gürgen, Melih Cemal Kuşhan, Weihua Li

    A thorough and critical review on Shear Thickening Fluids (STFs) is presented based on a literature survey. The rheological properties of STFs are discussed considering many factors affecting shear thickening behavior and the use of STFs in protective systems is reviewed. The main focus of this review is multi-phase STFs, relatively new to the literature (in the last five years). Multi-phase STFs include a second phase in suspensions and the influences of this additional phase on rheological behavior and protective applications are discussed extensively. Based on this extended review, STF do benefit protective applications, but the major contribution is not driven by the shear thickening behavior. Rather, STFs are responsible for the increase in friction along fabrics and enhanced fiber/yarn coupling in fabric based protective systems. As a result, of these effects, the load transfer is spread over a wider area and penetration depth is lowered in an impacted structure.

  • Role of free volume characteristics of polymer matrix in bulk physical properties of polymer nanocomposites: A review of positron annihilation lifetime studies
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-17
    S.K. Sharma, P.K. Pujari

    Polymer nanocomposites which have one or more nano-dimensional phases dispersed in polymer matrix show enhancement in bulk physical properties. In order to achieve the desired properties, a large number of polymer nanocomposites have been prepared by choosing different polymers and nanofillers. These studies showed that interfacial interaction between polymer molecules and nanofillers is the most important factor to achieve the synergistic effect towards enhancement in the bulk physical properties. The strong interfacial interaction also promotes the fine dispersion of nanofillers in a polymer matrix which consequently enables the preparation of polymer nanocomposites with higher loading of nanofillers. The polymer matrix constitutes a large volume fraction of polymer nanocomposites and hence the molecular packing of the polymer matrix itself plays a deterministic role in governing the physical properties of the nanocomposites. The strong interfacial interaction brings severe changes in the original molecular packing. In order to establish the structure-property relationships for polymer nanocomposites, characterization of molecular packing of polymer matrix in its nanocomposites is essential. In this aspect positron annihilation lifetime spectroscopy (PALS) is a highly suitable technique for characterization of free volume holes in polymers or polymer nanocomposites. The present review briefly describes the positron annihilation lifetime spectroscopy technique and relevant models for calculations of free volume hole’s size, density and their size distribution in polymer nanocomposites. We present a summary of the recent studies focussed on investigation of free volume structure (molecular packing) of polymer nanocomposites using PALS and its impact on transport, thermal and mechanical properties of the nanocomposites.

  • Macromolecular architectures through organocatalysis
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-15
    Shuangyan Hu, Junpeng Zhao, Guangzhao Zhang, Helmut Schlaad

    In virtue of the rising demand for metal-free polymeric materials, organocatalytic polymerization has emerged and blossomed unprecedentedly in the past 15 years into an appealing research area and a powerful arsenal for polymer synthesis. In addition to the inherent merits as being metal-free, small-molecule organocatalysts have also provided opportunities to develop alternative and, in many cases, more expedient synthetic approaches toward macromolecular architectures, that play a crucial role in shaping the properties of the obtained polymers. A majority of preliminary studies exploring for new catalysts, catalytic mechanisms and optimized polymerization conditions are extended to application of the catalytic systems on rational design and controlled synthesis of various macromolecular architectures. Such endeavors are described in this review, categorized by the architectural elements including chain structure (types, sequence and composition of monomeric units constituting the polymer chains), topological structure (the fashion different polymer chains are covalently attached to each other within the macromolecule) and functionality (position and amount of functional groups that endow the entire macromolecule with specific chemical, physico-chemical or biological properties).

  • Light-induced Release of Molecules from Polymers
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-07-04
    Pu Xiao, Jing Zhang, Jiacheng Zhao, Martina H. Stenzel

    The release of molecules from polymers upon light stimulus has been investigated for a range of applications in particular for drug delivery. In this review, the concept of light-induced release processes from polymers is summarized. Light-triggered processes can be divided into two approaches, the light induced degradation of polymers and the light-induced polarity change of the polymers. Functional groups that can enable the breakdown of the polymer or the cleavage of a linker between polymer and small molecule encompass coumarine and o-nitrobenzyl groups while azobenze and spyropyrane undergo reversible changes. Although the literature is dominated by these four compound classes, functional groups such as anthracene, pyrene, perylene, 2-diazo-1,2-naphthoquinone, and BODIPY can undergo similar changes. Degradation of polymers or simple polarity changes can trigger the release of small molecules such as drugs, but also gas molecules such as nitric oxide and macromolecules including DNA and proteins can be liberated upon light-trigger.

  • Micellization of synthetic and polysaccharides-based graft copolymers in aqueous media
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-06-13
    L.I. Atanase, J. Desbrieres, G. Riess

    This review highlights recent advances in the micellization of synthetic graft copolymers and those based on natural precursors, particularly polysaccharides. Synthesis and characterization of a broad range of architectures are discussed, along with different micellization procedures and fundamental micellar characteristics, such as morphology and size. Micelle formation by synthetic graft copolymers in aqueous media is examined in detail for different architectures of nonionic, ionic, and temperature and pH stimuli-responsive “double hydrophilic” copolymers. In this context, the problems associated with unimolecular micelles and the correlations between molecular characteristics are further addressed. In addition to backbone and side chain molecular weights, grafting density and topology are the major parameters that directly influence graft copolymer micellization. A similar overview is provided for graft copolymers based on polysaccharides, such as cellulose, chitosan, dextran, and starch. Finally, an outlook is given on the prospects for further development in this area.

  • Chlorine-resistance of reverse osmosis (RO) polyamide membranes
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-06-09
    Rhea Verbeke, Verónica Gómez, Ivo F.J. Vankelecom

    Polyamide (PA) reverse osmosis (RO) membranes suffer performance decay when exposed to oxidizing species, limiting their lifetime and increasing operation costs. This article aims at reviewing the effect of chlorine species on the performance and characteristics of PA-membranes. Experimental evidence supporting different competing mechanisms for chlorine-polymer interaction will be presented, together with the influence of operational parameters. Additionally, an overview of different modification methods that exist to render PA-membranes more chlorine-resistant is given.

  • Main-chain poly(phosphoester)s: History, syntheses, degradation, bio-and flame-retardant applications
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-05-31
    Kristin N. Bauer, Hisaschi T. Tee, Maria M. Velencoso, Frederik R. Wurm

    Nature on planet earth is dominated by poly(phosphoester)s (PPEs). They structure and determine life in the form of deoxy- and ribonucleic acid (DNA & RNA), and, as pyrophosphates, they store chemical energy in organisms. Polymer chemistry, however, is dominated by the non-degradable polyolefins and degradable polycarboxylic esters (PCEs) produced on a large scale today. Recent work has illustrated the potential of PPEs for future applications beyond flame-retardancy, the main application of PPEs today, and provided a coherent vision to implement this classic biopolymer in modern applications that demand biocompatibility and degradability as well as the possibility to adjust the properties to individual needs. This comprehensive review summarizes synthetic protocols to PPEs, their applications in biomedicine, e.g., as biodegradable drug carrier or in tissue engineering, and their flame retardant properties. We highlight recent developments that may make phosphorus-based polymers attractive materials for various future applications.

  • Vinylidene fluoride- and trifluoroethylene-containing fluorinated electroactive copolymers. How does chemistry impact properties?
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-05-15
    Thibaut Soulestin, Vincent Ladmiral, Fabrice Domingues Dos Santos, Bruno Améduri

    Fluoropolymers are attractive niche polymers used in high added value materials for high-tech applications in aerospace, electronics, coatings, membranes, cables, and the automotive industries. Among them, VDF- and TrFE-based copolymers exhibit remarkable electroactive properties allowing their incorporation into a wide range of devices such as printed memories, sensors, actuators, artificial muscles, and energy storage devices. In a first section, a detailed overview of semi-crystalline poly(VDF-co-TrFE) copolymers and of their ferroelectric (FE) properties from the point of view of polymer chemists is supplied. In addition to the polymer microstructure that may sometimes be controlled or influenced by the synthesis strategies, physical properties such as the phase transitions, and electroactivity are also affected by processing, such as annealing for example, and film thickness for example. Building on the conclusions and understanding obtained from the first section, the effect of the introduction of a termonomer (leading to poly(VDF-ter-TrFE-ter-M) terpolymers) is detailed in a second section of this review. Modifying the terpolymer chain microstructure has a major impact on the crystalline phase of the terpolymers that may result in a relaxor-ferroelectric behavior (RFE). The distribution of the termonomer along the polymer chain, the capacity of the termonomer units to enter the crystal lattice, as well as its dipole moment govern in large part the terpolymer electroactive properties. Poly(VDF-ter-TrFE-ter-CFE) and poly(VDF-ter-TrFE-ter-CTFE) terpolymers appeared to be the best candidates for RFE properties and were thus the most studied. In two following sections, the block or graft architectures of VDF- and TrFE- based copolymers, and the various crosslinking strategies used so far for such copolymers are described. Chemical modification is indeed a very powerful tool to tune electroactive properties of copolymers or to impart additional properties. Finally, in the last section, a few examples of emerging applications for these fluorinated electroactive polymers (EAPs) are briefly discussed. This review aims to provide a comprehensive report on the use of polymer chemistry as a tool to produce better electroactive fluorinated polymers, and highlights possible opportunities and perspectives for future progress in this field. Research in this interdisciplinary field requires different kinds of expertise, ranging from organic and polymer chemistries, polymer films engineering, physics of semi-crystalline polymers and electroactivity, to the design and fabrication of electronic devices.

  • Theoretical modeling and simulations of self-assembly of copolymers in solution
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-05-03
    Qian Zhang, Jiaping Lin, Liquan Wang, Zhanwen Xu

    Self-assembly of copolymers in solution is a promising way to prepare novel materials. An accurate control over the self-assembly of copolymers in solution requires a profound understanding about the related thermodynamic rules and kinetic mechanisms. Theoretical modeling and simulation play an increasingly important role in characterizing the structure details and the formation process of polymer assemblies. In this review, we first introduce theoretical modeling and simulation methods that have been applied to investigate the self-assembly of copolymers in solution, including particle-based methods, field-theoretical methods and hybrid modeling methods Then, the application of these methods for the self-assembly of linear block copolymers in solution is highlighted, including the thermodynamic rules and kinetic mechanisms underlying the formation of self-assembled structures. Furthermore, the simulation works of the self-assembly of branched copolymer systems, including graft copolymers, star-like copolymers, dendritic copolymers and bottle-brush copolymers, are addressed. In addition to the one-component polymer systems, simulation investigations of polymer mixture systems are discussed, both the polymer/polymer systems and polymer/nanoparticle systems are considered. Finally, perspectives on the theoretical modeling and simulation in the field of self-assembly of copolymers in solution are presented in the section of concluding remarks and outlook.

  • The aza-Michael reaction as an alternative strategy to generate advanced silicon-based (macro)molecules and materials
    Prog. Polym. Sci. (IF 25.766) Pub Date : 2017-02-20
    Aymeric Genest, Daniel Portinha, Etienne Fleury, François Ganachaud

    Aza-Michael reaction is a simple and accessible addition reaction performed at moderate temperature, possibly without a catalyst and without releasing by-products. Its versatility allows designing specific structures thanks to the availability of a multitude of Michael acceptors and Michael donors. The reaction rate of the aza-Michael reaction can be improved by adding different co-reactants (polar protic solvents, catalysts) and/or adjusting the external energy sources (e.g. moderate to high temperatures or high pressures). Here, we show that this addition reaction is efficient for modifying or curing silicon-containing molecules, oligomers and polymers. The pros and cons of applying the aza-Michael reaction to silicon-containing molecules (including alkoxysilanes and PDMS) are highlighted. A large variety of intermediates such as coupling agents, reactive diluents, and sol-gel precursors prepared by the aza-Michael reaction are presented. Finally, applications of these, including products ranging from functional silicone intermediates to soft (unfilled) elastomers, are reported.

Some contents have been Reproduced with permission of the American Chemical Society.
Some contents have been Reproduced by permission of The Royal Society of Chemistry.
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