Topical Collection "Design and Synthesis of Polymers"

Editor

Collection Editor
Prof. Shin-ichi Yusa

Department of Materials Science and Chemistry, University of Hyogo, 2167 Shosha, Himeji, Hyogo, Japan
Website | E-Mail
Phone: +81-79-267-4954
Fax: +81 79 266 8868
Interests: controlled/living radical polymerization; RAFT; TERP; water-soluble polymer; self-organization; polymer micelle; bioconjugate polymer

Topical Collection Information

Dear Colleagues,

It is well-known that polymer functions strongly depend on their design and structure. The design and synthesis of polymers are very important for desired properties. Commonly, most polymers are synthesized by the following methods: radical, anionic, cationic, condensation, ring opening, and coordination polymerizations. Unfortunately, these synthetic polymer structures are not well-controlled compared with biopolymers, such as polypeptide, DNA, RNA, and so on. We cannot precisely control molecular weight, molecular weight distribution, monomer sequence, and tacticity. Recently, controlled polymerization methods have been developed to achieve well-controlled structured polymers with defined molecular weight and narrow molecular weight distribution. However, this is unsatisfactory compared with biopolymers. Especially, monomer sequence and tacticity controls constitute difficult challenges. Additionally, there are various design of polymers, such as linear polymer, random copolymer, alternative copolymer, block copolymer, branched polymer, graft copolymer, star-shape copolymer, mikto−arm copolymer, dendrimer, and so on. These designs are the key points of the functions.

This collection is concerned with the design and synthesis of polymers. We hope to share new concept designs of polymers, polymer synthesis methods, and analysis of polymerization mechanisms. Both original contributions and reviews are welcome.

Prof. Shin-ichi Yusa
Collection 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 papers will be peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the collection 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 monthly 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 1500 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

  • Linear polymer
  • Random copolymer
  • Alternative copolymer
  • Branched polymer
  • Block copolymer
  • Conjugated polymer
  • Graft copolymer
  • Star-shaped polymer
  • Dendrimer
  • Radical polymerization
  • Anionic polymerization
  • Cationic polymerization
  • Condensation polymerization
  • Ring opening polymerization
  • Coordination polymerization
  • Polyaddition
  • Addition condensation
  • Living polymerization
  • Polymerization mechanism
  • Monomer sequence control
  • Tactility
  • Copolymerization
  • Photo-polymerization
  • New concept of polymerization

Published Papers (6 papers)

2019

Open AccessArticle Synthesis and Photoinduced Anisotropy of Polymers Containing Nunchaku-Like Unit with an Azobenzene and a Mesogen
Polymers 2019, 11(4), 600; https://doi.org/10.3390/polym11040600
Received: 14 March 2019 / Revised: 25 March 2019 / Accepted: 25 March 2019 / Published: 2 April 2019
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Abstract
A series of polymers containing nunchaku-like unit with an azo chromophore and a mesogen group was successfully prepared and photoinduced anisotropy of the obtained polymers was minutely investigated. Firstly, monomers containing nunchaku-like unit with an azo chromophore and a mesogen group linked by [...] Read more.
A series of polymers containing nunchaku-like unit with an azo chromophore and a mesogen group was successfully prepared and photoinduced anisotropy of the obtained polymers was minutely investigated. Firstly, monomers containing nunchaku-like unit with an azo chromophore and a mesogen group linked by flexible group were synthesized. The structure of the monomers was confirmed via NMR COSY spectra. Subsequently, the obtained monomers were polymerized into corresponding polymers through RAFT polymerization. The prepared polymer samples were characterized through NMR, FTIR, gel permeation chromatography (GPC), and UV-vis testing while the thermal properties of the samples were investigated through differential scanning calorimeter (DSC) and thermogravimetric analysis (TGA) measurements. The photoinduced isomerization of the polymers, which was researched in situ via measuring UV-vis spectra of the polymer solutions and spin-coated films under irradiation with 450 nm light or putting in darkness, demonstrated the rapid trans-cis-trans isomerization of the polymers. When irradiated with a linearly polarized light, significant photoinduced birefringence and dichroism were observed, suggesting photoinduced isomerization of azobenzene can drive orientation of mesogen in the system. This study blazes a way to design the optical materials with light-controllable birefringence and dichroism. Full article
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Open AccessArticle Characteristics and Mechanism of Vinyl Ether Cationic Polymerization in Aqueous Media Initiated by Alcohol/B(C6F5)3/Et2O
Polymers 2019, 11(3), 500; https://doi.org/10.3390/polym11030500
Received: 28 February 2019 / Revised: 11 March 2019 / Accepted: 11 March 2019 / Published: 14 March 2019
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Abstract
Aqueous cationic polymerizations of vinyl ethers (isobutyl vinyl ether (IBVE), 2-chloroethyl vinyl ether (CEVE), and n-butyl vinyl ether (n-BVE)) were performed for the first time by a CumOH/B(C6F5)3/Et2O initiating system in an [...] Read more.
Aqueous cationic polymerizations of vinyl ethers (isobutyl vinyl ether (IBVE), 2-chloroethyl vinyl ether (CEVE), and n-butyl vinyl ether (n-BVE)) were performed for the first time by a CumOH/B(C6F5)3/Et2O initiating system in an air atmosphere. The polymerization proceeded in a reproducible manner through the careful design of experimental conditions (adding initiator, co-solvents, and surfactant or decreasing the reaction temperature), and the polymerization characteristics were systematically tested and compared in the suspension and emulsion. The significant difference with traditional cationic polymerization is that the polymerization rate in aqueous media using B(C6F5)3/Et2O as a co-initiator decreases when the temperature is lowered. The polymerization sites are located on the monomer/water surface. Density functional theory (DFT) was applied to investigate the competition between H2O and alcohol combined with B(C6F5)3 for providing a theoretical basis. The effectiveness of the proposed mechanism for the aqueous cationic polymerization of vinyl ethers using CumOH/B(C6F5)3/Et2O was confirmed. Full article
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Open AccessArticle Effects of End-Caps on the Atropisomerization, Polymerization, and the Thermal Properties of ortho-Imide Functional Benzoxazines
Polymers 2019, 11(3), 399; https://doi.org/10.3390/polym11030399
Received: 5 February 2019 / Revised: 20 February 2019 / Accepted: 22 February 2019 / Published: 1 March 2019
Cited by 1 | PDF Full-text (3682 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
A new type of atropisomerism has recently been discovered in 1,3-benzoxazines, where the intramolecular repulsion between negatively charged oxygen atoms on the imide and the oxazine ring hinders the rotation about the C–N bond. The imide group offers a high degree of flexibility [...] Read more.
A new type of atropisomerism has recently been discovered in 1,3-benzoxazines, where the intramolecular repulsion between negatively charged oxygen atoms on the imide and the oxazine ring hinders the rotation about the C–N bond. The imide group offers a high degree of flexibility for functionalization, allowing a variety of functional groups to be attached, and producing different types of end-caps. In this work, the effects of end-caps on the atropisomerism, thermally activated polymerization of ortho-imide functional benzoxazines, and the associated properties of polybenzoxazines have been systematically investigated. Several end-caps, with different electronic characteristics and rigidities, were designed. 1H and 13C nuclear magnetic resonance (NMR) spectroscopy and density functional theory (DFT) calculations were employed to obtain structural information, and differential scanning calorimetry (DSC) and in situ Fourier transform infrared (FT-IR) spectroscopy were also performed to study the thermally activated polymerization process of benzoxazine monomers. We demonstrated that the atropisomerization can be switched on/off by the manipulation of the steric structure of the end-caps, and polymerization behaviors can be well-controlled by the electronic properties of the end-caps. Moreover, a trade-off effect were found between the thermal properties and the rigidity of the end-caps in polybenzoxazines. Full article
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Open AccessCommunication Synthesis of Polyazobenzenes Exhibiting Photoisomerization and Liquid Crystallinity
Polymers 2019, 11(2), 348; https://doi.org/10.3390/polym11020348
Received: 7 January 2019 / Revised: 9 February 2019 / Accepted: 12 February 2019 / Published: 17 February 2019
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Abstract
While only a few studies have investigated the synthesis of main chain-type polyazobenzenes, they continue to draw an increasing amount of attention owing to their industrial applications in holography, dyes, and functional adhesives. In this study, dibromoazobenzene was prepared as a monomer for [...] Read more.
While only a few studies have investigated the synthesis of main chain-type polyazobenzenes, they continue to draw an increasing amount of attention owing to their industrial applications in holography, dyes, and functional adhesives. In this study, dibromoazobenzene was prepared as a monomer for constructing azo-based π-conjugated polymers. Miyaura–Suzuki cross-coupling polymerization was conducted to develop copolymers containing an azobenzene unit as a photoisomerization block and a pyrimidine-based liquid crystal generator block. The prepared polymers exhibited thermotropic liquid crystallinity and underwent cis and trans photoisomerization upon irradiation with ultraviolet and visible light. Furthermore, the photoisomerization behavior was examined using optical absorption spectroscopy and synchrotron X-ray diffraction spectrometry. Full article
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Open AccessArticle Hyperbranched Polycaprolactone through RAFT Polymerization of 2-Methylene-1,3-dioxepane
Polymers 2019, 11(2), 318; https://doi.org/10.3390/polym11020318
Received: 16 January 2019 / Revised: 4 February 2019 / Accepted: 4 February 2019 / Published: 13 February 2019
Cited by 1 | PDF Full-text (2017 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Hyperbranched polycaprolactone with controlled structure was synthesized by reversible addition-fragmentation chain transfer radical ring-opening polymerization along with self-condensed vinyl polymerization (SCVP) of 2-methylene-1,3-dioxepane (MDO). Vinyl 2-[(ethoxycarbonothioyl) sulfanyl] propanoate (ECTVP) was used as polymerizable chain transfer agent. Living polymerization behavior was proved via pseudo [...] Read more.
Hyperbranched polycaprolactone with controlled structure was synthesized by reversible addition-fragmentation chain transfer radical ring-opening polymerization along with self-condensed vinyl polymerization (SCVP) of 2-methylene-1,3-dioxepane (MDO). Vinyl 2-[(ethoxycarbonothioyl) sulfanyl] propanoate (ECTVP) was used as polymerizable chain transfer agent. Living polymerization behavior was proved via pseudo linear kinetics, the molecular weight of polymers increasing with conversion and successful chain extension. The structure of polymers was characterized by 1H NMR spectroscopy, tripe detection gel permeation chromatography, and differential scanning calorimetry. The polymer composition was shown to be able to tune to vary the amount of ester repeat units in the polymer backbone, and hence determine the degree of branching. As expected, the degree of crystallinity was lower and the rate of degradation was faster in cases of increasing the number of branches. Full article
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Open AccessArticle Design and Synthesis of a Cyclic Double-Grafted Polymer Using Active Ester Chemistry and Click Chemistry via A “Grafting onto” Method
Polymers 2019, 11(2), 240; https://doi.org/10.3390/polym11020240
Received: 4 January 2019 / Revised: 21 January 2019 / Accepted: 24 January 2019 / Published: 1 February 2019
PDF Full-text (2710 KB) | HTML Full-text | XML Full-text | Supplementary Files
Abstract
Combing active ester chemistry and click chemistry, a cyclic double-grafted polymer was successfully demonstrated via a “grafting onto” method. Using active ester chemistry as post-functionalized modification approach, cyclic backbone (c-P2) was synthesized by reacting propargyl amine with cyclic precursor (poly(pentafluorophenyl 4-vinylbenzoate), [...] Read more.
Combing active ester chemistry and click chemistry, a cyclic double-grafted polymer was successfully demonstrated via a “grafting onto” method. Using active ester chemistry as post-functionalized modification approach, cyclic backbone (c-P2) was synthesized by reacting propargyl amine with cyclic precursor (poly(pentafluorophenyl 4-vinylbenzoate), c-PPF4VB6.5k). Hydroxyl-containing polymer double-chain (l-PS-PhOH) was prepared by reacting azide-functionalized polystyrene (l-PSN3) with 3,5-bis(propynyloxy)phenyl methanol, and further modified by azide group to generate azide-containing polymer double-chain (l-PS-PhN3). The cyclic backbone (c-P2) was then coupled with azide-containing polymer double-chain (l-PS-PhN3) via CuAAC reaction to construct a novel cyclic double-grafted polymer (c-P2-g-Ph-PS). This research realized diversity and complexity of side chains on cyclic-grafted polymers, and this cyclic double-grafted polymer (c-P2-g-Ph-PS) still exhibited narrow molecular weight distribution (Mw/Mn < 1.10). Full article
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Polymers EISSN 2073-4360 Published by MDPI AG, Basel, Switzerland RSS E-Mail Table of Contents Alert
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