Precision Polymer Synthesis

A special issue of Polymers (ISSN 2073-4360).

Deadline for manuscript submissions: closed (20 May 2018) | Viewed by 22471

Special Issue Editor

Centre for Advanced Macromolecular Design and Australian Centre for Nanomedicine, School of Chemical Engineering, University of New South Wales, Sydney 2052, Australia
Interests: polymer synthesis; green chemistry; photopolymerization; visible light catalysis; coordination network polymers; biomaterials

Special Issue Information

Dear Colleagues,

Natural polymers, such as peptides and nucleic acids, are uniform polymers with precise monomer sequence and stereoregularity that provides for unique biological functions, which include motifs for molecular recognition (RGD tripeptide), biocatalysis (enzyme) and data storage (DNA). Many scientists have tried to emulate the precision of natural polymers with synthetic polymers owing to the additional opportunities provided by the broad chemical diversity of monomers, well-established polymerization processes, and their relatively simple manipulation. In the last 50 years, significant efforts have been devoted in the development of “living” polymerisation techniques, including anionic/cationic, controlled radical, ring-opening metathesis and coordination polymerizations. By using these techniques well-defined polymers are able to be synthesised with various architectures and controlled tacticity. Although these mechanisms usually allow fast and large scale synthesis of polymers, substantial experimental defects are still present, such as lack of precision, statistical distribution of monomers and the need for multiple purification steps. Attempts to produce synthetic materials with the structural sophistication and precision found in nature still remains elusive.

This Special Issue focuses on the current research frontiers of precision polymer synthesis and its characterization. Papers (research articles or reviews) are sought to discuss the latest research in the area or summarize selected areas of the field. The scope encompasses the precise synthesis and characterization of polymers using various polymerization techniques regardless of chain-growth or step-growth approaches, and synthetic chemical tools (click chemistry, diels-alder reactions and iterative exponential growth, etc), as well as separation systems (automated flash chromatography and repetitive column purification, etc). Of additional interests are new polymer structures and functions resulting from the synthesized polymer materials featuring specific physical and chemical properties and self-assembling behaviours, and new insights on the structure-properties relationships leading to potential applications.

Dr. Jiangtao Xu
Guest Editor

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

  • Controlled/“living” polymerization
  • Sequence-controlled polymers
  • Stereo-regulated polymers
  • Mechanism of polymerization
  • Polymerization kinetics
  • Polymer topological architectures
  • Flow polymer synthesis
  • Multiblock copolymers
  • Polymer functionalization

Published Papers (4 papers)

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Research

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15 pages, 5588 KiB  
Article
A Facile Approach towards Fluorescent Nanogels with AIE-Active Spacers
by Meiran Feng, Laiping Fang, Fujun Guan, Siying Huang, Yinwei Cheng, Yancui Liang and Hefeng Zhang
Polymers 2018, 10(7), 722; https://doi.org/10.3390/polym10070722 - 01 Jul 2018
Cited by 6 | Viewed by 4594
Abstract
A facile and efficient approach for design and synthesis of organic fluorescent nanogels has been developed by using a pre-synthesized polymeric precursor. This strategy is achieved by two key steps: (i) precise synthesis of core–shell star-shaped block copolymers with crosslinkable AIEgen-precursor (AIEgen: aggregation [...] Read more.
A facile and efficient approach for design and synthesis of organic fluorescent nanogels has been developed by using a pre-synthesized polymeric precursor. This strategy is achieved by two key steps: (i) precise synthesis of core–shell star-shaped block copolymers with crosslinkable AIEgen-precursor (AIEgen: aggregation induced emission luminogen) as pending groups on the inner blocks; (ii) gelation of the inner blocks by coupling the AIEgen-precursor moieties to generate AIE-active spacers, and thus, fluorescent nanogel. By using this strategy, a series of star-shaped block copolymers with benzophenone groups pending on the inner blocks were synthesized by grafting from a hexafunctional initiator through atom transfer radical copolymerization (ATRP) of 4-benzoylphenyl methacrylate (BPMA) or 2-(4-benzoylphenoxy)ethyl methacrylate (BPOEMA) with methyl methacrylate (MMA) and tert-butyldimethylsilyl-protected 2-hydroxyethyl methacrylate (ProHEMA) followed by a sequential ATRP to grow PMMA or PProHEMA. The pendent benzophenone groups were coupled by McMurry reaction to generate tetraphenylethylene (TPE) groups which served as AIE-active spacers, affording a fluorescent nanogel. The nanogel showed strong emission not only at aggregated state but also in dilute solution due to the strongly restricted inter- and intramolecular movement of TPE moiety in the crosslinked polymeric network. The nanogel has been used as a fluorescent macromolecular additive to fabricate fluorescent film. Full article
(This article belongs to the Special Issue Precision Polymer Synthesis)
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9 pages, 21238 KiB  
Article
Synthesis of Polystyrene Particles with Precisely Controlled Degree of Concaveness
by Wenhua Jing, Sinan Du and Zexin Zhang
Polymers 2018, 10(4), 458; https://doi.org/10.3390/polym10040458 - 21 Apr 2018
Cited by 13 | Viewed by 7657
Abstract
Shape is an essential property of polymeric particles. Herein, we propose a simple method to synthesize polymeric particles with a well-controlled concave shape. Our method takes advantage of the powerful seeded emulsion polymerization strategy with the well-known principle of “like dissolves like” in [...] Read more.
Shape is an essential property of polymeric particles. Herein, we propose a simple method to synthesize polymeric particles with a well-controlled concave shape. Our method takes advantage of the powerful seeded emulsion polymerization strategy with the well-known principle of “like dissolves like” in solvent chemistry. We first prepared polystyrene (PS) particles with a single dimple by seeded emulsion polymerization. Then the dimpled PS particles were dispersed in a dimethylformamide (DMF) and water mixture. Consequently, the non-crosslinked polymer chains inside the particle were dissolved by DMF, a good solvent for PS, and the PS chains migrated out of the particle, causing buckling of the dimple and enlargement of the concave. By systematic change of the fraction of DMF in the solvent mixture, we changed the amount of the dissolved PS chains, and achieved polymeric particles with precisely tuned degree of concaveness. These concave particles were found to readily self-assemble, driven by polymer-induced depletion interaction. The concave PS particles reported here provide potential building blocks for self-assembled polymeric materials, and new model systems for condensed matter research. Full article
(This article belongs to the Special Issue Precision Polymer Synthesis)
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14 pages, 14305 KiB  
Article
A Study of the Polycondensation of (Tetrahydroxy)(Tetraaryl)Cyclotetrasiloxanes under Equilibrium and Non-Equilibrium Conditions in the Presence and Absence of Montmorillonite
by Nataliya N. Makarova, Yury I. Lyakhovetsky, Irina M. Petrova, Fedor M. Dolgushin, Nikolai S. Ikonnikov, Alexander S. Peregudov, Tatyana V. Strelkova and Zinaida S. Klemenkova
Polymers 2018, 10(4), 422; https://doi.org/10.3390/polym10040422 - 09 Apr 2018
Cited by 3 | Viewed by 3719
Abstract
Oligo- and polycyclosiloxanes were obtained by the polycondensation of (tetrahydroxy)(tetraaryl)cyclotetrasiloxanes in equilibrium and non-equilibrium conditions in the presence and absence of montmorillonite (MMT). Their composition and the structures of their components were investigated by infrared (IR) spectroscopy, 29Si nuclear magnetic resonance (NMR) [...] Read more.
Oligo- and polycyclosiloxanes were obtained by the polycondensation of (tetrahydroxy)(tetraaryl)cyclotetrasiloxanes in equilibrium and non-equilibrium conditions in the presence and absence of montmorillonite (MMT). Their composition and the structures of their components were investigated by infrared (IR) spectroscopy, 29Si nuclear magnetic resonance (NMR) spectroscopy, atmospheric pressure chemical ionization (APCI) mass spectrometry, powder X-ray diffraction (XRD), and gel-penetrating chromatography (GPC). Also, a comparison of polymers formed in the presence of MMT and via anionic polymerization was performed showing differences in their structures. Full article
(This article belongs to the Special Issue Precision Polymer Synthesis)
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Review

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26 pages, 7931 KiB  
Review
Biodegradable Polymeric Architectures via Reversible Deactivation Radical Polymerizations
by Fengyu Quan, Aitang Zhang, Fangfang Cheng, Liang Cui, Jingquan Liu and Yanzhi Xia
Polymers 2018, 10(7), 758; https://doi.org/10.3390/polym10070758 - 09 Jul 2018
Cited by 8 | Viewed by 5353
Abstract
Reversible deactivation radical polymerizations (RDRPs) have proven to be the convenient tools for the preparation of polymeric architectures and nanostructured materials. When biodegradability is conferred to these materials, many biomedical applications can be envisioned. In this review, we discuss the synthesis and applications [...] Read more.
Reversible deactivation radical polymerizations (RDRPs) have proven to be the convenient tools for the preparation of polymeric architectures and nanostructured materials. When biodegradability is conferred to these materials, many biomedical applications can be envisioned. In this review, we discuss the synthesis and applications of biodegradable polymeric architectures using different RDRPs. These biodegradable polymeric structures can be designed as well-defined star-shaped, cross-linked or hyperbranched via smartly designing the chain transfer agents and/or post-polymerization modifications. These polymers can also be exploited to fabricate micelles, vesicles and capsules via either self-assembly or cross-linking methodologies. Nanogels and hydrogels can also be prepared via RDRPs and their applications in biomedical science are also discussed. In addition to the synthetic polymers, varied natural precursors such as cellulose and biomolecules can also be employed to prepare biodegradable polymeric architectures. Full article
(This article belongs to the Special Issue Precision Polymer Synthesis)
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