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  • Transparent and super-gas-barrier PET film with surface coated by a polyelectrolyte and Borax
    Polym. J. (IF 2.145) Pub Date : 2018-01-15
    Mengze Lu, Sheng Huang, Shou Chen, Qing Ju, Min Xiao, Xiaohua Peng, Shuanjin Wang, Yuezhong Meng

    Thin films of polyacrylic acid (PAA), 4,4‘-diphenylmethane diisocyanate (MDI) and borax were separately grown on a poly (ethylene terephthalate) (PET) film to afford a transparent film material with super gas barrier performance. Unlike electrostatic interactions or clay-loaded barrier thin films, which were easily peeled when subjected to exoteric force, excellent peel strength was obtained due to the formation of high density urethane chemical bonds. The gas vapor barrier value is dramatically decreased to the detection limit of commercial instrumentation (<0.005 cc/m2/day). These outstanding performances are attributed to the reaction between sodium metaborate and PAA, which is confirmed using online infrared radiation (IR) and X-ray photoelectron spectroscopy (XPS). The XPS of the multilayer film revealed that borax can permeate the PAA thin layer to completely crosslink the carboxyl group of PAA. The gas barrier properties are obviously improved by the permeating borax solution. In particular, compared to commercial PET film, the oxygen transmission rate (OTR) is reduced from 75 to <0.005 cc/m2/day. Moreover, the OTR value is almost same as that of poly(ethylene-co-vinyl alcohol) (EVOH) film, which is currently the best gas barrier plastic. Therefore, the PET/MDI/PAA/borax composite films show great potential for various packaging materials due to their excellent oxygen and moisture barrier characteristics, as well as other performance.

    更新日期:2018-01-15
  • Synthesis of CO2-derived polycarbonates with high glass transition temperatures
    Polym. J. (IF 2.145) Pub Date : 2018-01-15
    Rie Arai, Keitaro Seto, Andrew Bell, Hiroshi Sugimoto

    To synthesize CO2-derived polycarbonates with high Tg values, epoxides having rigid and bulky 2-norbornyl or 1-adamantyl substituents were selected as comonomers. The alternating copolymer obtained from 1-adamantylethylene oxide showed a Tg above 150 °C. This is the highest Tg among those observed for alternating copolymers obtained from CO2 and a terminal epoxide.

    更新日期:2018-01-15
  • Synthesis and characterization of poly(2,6-dialkoxy-1,5-naphthylene)s with low dielectric constants
    Polym. J. (IF 2.145) Pub Date : 2018-01-15
    Li-Che Hsu, Min Chi Yang, Tomoya Higashihara, Wen-Chang Chen, Mitsuru Ueda

    An efficient method to decrease dielectric constant (ε) of poly(2,6-dihydroxy-1,5-naphthylene) (PDHN) by introducing bulky alkyl side chains was reported. Poly(2,6-dialkoxy-1,5-naphthylene)s (PDANs) were prepared by the O-alkylation of PDHN with alkyl halides. The ε values of PDANs at 10 GHz decreased as the length and size of side chains increased. Especially, PDCHMN exhibited the lowest dielectric constant (ε = 2.29). The ε value results were also supported by refractive index measurement.

    更新日期:2018-01-15
  • Synthesis, properties and structure of borafluorene-based conjugated polymers with kinetically and thermodynamically stabilized tetracoordinated boron atoms
    Polym. J. (IF 2.145) Pub Date : 2018-01-09
    Takuya Matsumoto, Shunichiro Ito, Kazuo Tanaka, Yoshiki Chujo

    Herein, borafluorene-conjugated polymers with a dibromoborafluorene monomer and various boronic acid ester comonomers are reported. By employing the Suzuki−Miyaura cross-coupling reaction, a series of copolymers was prepared with the boron atoms in tetracoordinated states. Based on comparison to the optical properties of gallafluorene copolymers, higher luminescence quantum yields were obtained from the synthesized borafluorene copolymers due to the weak spin-orbit interaction of boron compared to that of gallium. Additionally, the results from the electrochemical measurements indicated that the electron-withdrawing property of the boron atoms led to stabilization of the lowest unoccupied molecular orbitals (LUMOs) of the borafluorene copolymers. In the X-ray diffraction profiles, significant peaks originating from π−π stacking and assembly of the side chains were observed. The borafluorene copolymers were more crystalline than the gallafluorene polymers.

    更新日期:2018-01-09
  • A facile method for the controlled polymerization of biocompatible and thermoresponsive oligo(ethylene glycol) methyl ether methacrylate copolymers
    Polym. J. (IF 2.145) Pub Date : 2018-01-09
    Teresa Alejo, Martín Prieto, Hugo García-Juan, Vanesa Andreu, Gracia Mendoza, Víctor Sebastián, Manuel Arruebo

    Photochemically controlled ATRP-like polymerization is successfully used to prepare a thermoresponsive copolymer of oligo(ethylene glycol) methyl ether methacrylate (OEGMA) and di(ethylene glycol) methyl ether methacrylate (MEO2MA). The photochemically controlled method described here provides good control over the polymer structure, architecture, and properties. This photopolymerization renders polymers with narrow molecular weight distributions (Mw/Mn = 1.3) and high monomer conversions (>90%) while using a very low iridium-based catalyst concentration (25 ppm). In addition, the reaction rate of this polymerization is fast, reaching 50% monomer conversion in less than 1 h of reaction. The lower critical solution temperature (LCST) of the prepared polymer was also adjusted to be in the range of physiological temperatures, undergoing a coil-to-globule transition at 43 °C. In addition, the resulting polymer showed no cytotoxicity on four mammalian cell lines at the highest concentration tested (0.4 mg/ml), which highlights its potential use in different biomedical applications.

    更新日期:2018-01-09
  • 50th volume anniversary of Polymer Journal
    Polym. J. (IF 2.145) Pub Date : 2018-01-05
    Takashi Kato

    50th volume anniversary of Polymer Journal50th volume anniversary of <i>Polymer Journal</i>, Published online: 05 January 2018; doi:10.1038/pj.2017.7350th volume anniversary of Polymer Journal

    更新日期:2018-01-05
  • Producing a magnetically anisotropic soft material: synthesis of iron oxide nanoparticles in a carrageenan/PVA matrix and stretching of the hybrid gelatinous bulk
    Polym. J. (IF 2.145) Pub Date : 2017-12-22
    Rie Sakai, Yoshikuni Teramoto, Yoshiyuki Nishio

    Abstract We propose a method for preparing magnetically anisotropic soft materials that includes chemical loading (in situ synthesis) of iron oxide nanoparticles in a matrix composed of κ-carrageenan (Car) and poly(vinyl alcohol) (PVA) followed by mechanical stretching of the hybrid in a wet process. Anionic Car was used to accommodate the iron oxide nanoparticles and was blended in advance with PVA, which has the ability of high orientation. Scanning electron microscopy revealed that the loaded granular iron oxide nanoparticles (50–100 nm) formed elliptical clusters upon stretching of the hybrid composite. Wide-angle X-ray diffraction measurements indicated that the PVA constituent was oriented in the draw direction. With the orientation of the composite matrix, the incorporated iron oxide nanoparticles gathered to form elliptical clusters. The drawn samples showed different amplitudes in the magnetization (M|| > M⊥) when measured in two setups in which the applied field was parallel (||) or perpendicular (⊥) to the draw direction. The specific responses of the drawn sheets to an external magnetic stimulus were visualized and were reasonably attributed to an effect of the magnetic anisotropy created by the preferred orientation of the nanoparticle aggregates. Graphical abstract We prepared magnetically anisotropic soft materials by in situ synthesis of iron oxide nanoparticles in a matrix composed of κ-carrageenan and PVA followed by mechanical stretching of the hybrid in a wet process. With the orientation of the composite matrix, the incorporated iron oxide nanoparticles gathered to form elliptical clusters. The drawn samples showed different magnetizations depending on the direction of magnetic field application. The specific responses were macroscopically visualized and were attributed to the magnetic anisotropy created by the preferred orientation of the nanoparticle aggregates.

    更新日期:2017-12-22
  • Alkylated alkali lignin for compatibilizing agents of carbon fiber-reinforced plastics with polypropylene
    Polym. J. (IF 2.145) Pub Date : 2017-12-22
    Hiroki Sakai, Kosuke Kuroda, Shiori Muroyama, Takayuki Tsukegi, Ryohei Kakuchi, Kenji Takada, Ayano Hata, Ryosuke Kojima, Tomoki Ogoshi, Masaaki Omichi, Kazuaki Ninomiya, Kenji Takahashi

    As an alternative to petroleum-based compatibilizing agents, we developed lignin derivatives for compatibilizing agents of carbon fiber-reinforced plastics that have thermoplasticity. In this study, alkyl chains were introduced into alkali lignin at various ratios to optimize the compatibility of the lignin derivatives with both polypropylene and carbon fiber. The interfacial shear strength between the two materials was improved from 8.2 to 17.2 MPa by mixing with the optimized lignin derivative. The value is comparable to that achieved with a typical petroleum-based compatibilizing agent (18.3 MPa).

    更新日期:2017-12-22
  • Synthesis of non-ionic poly(ester-sulfone) via low-temperature polycondensation for anode-selective electrophoretic deposition and subsequent photo cross-linking
    Polym. J. (IF 2.145) Pub Date : 2017-12-22
    Yoshifumi Matsumoto, Akinori Takasu

    Abstract Non-ionic aliphatic polymers containing ester and sulfonyl moieties, poly(ester-sulfones) were found to show anode-selective electrophoresis under electrophoretic deposition (EPD) conditions. Various polyesters containing a sulfide linkage were prepared via low-temperature polycondensation using scandium trifluoromethanesulfonate [Sc(OTf)3] as a catalyst in order to clarify the relationship between the chemical structure and the electrophoresis. Subsequently, oxone oxidation was carried out in order to obtain the expected saturated and unsaturated poly(ester-sulfone)s, and electrophoretic deposition (EPD) of the poly(ester-sulfone) onto stainless steel was performed. For unsaturated poly(ester-sulfone) onto stainless steel, subsequent UV irradiation cured the deposited film, improving the peeling strength of the coating. Graphical Abstract Various polyesters containing a sulfide linkage were prepared via low-temperature polycondensation using scandium trifluoromethanesulfonate [Sc(OTf)3] as a catalyst in order to clarify the relationship between the chemical structure and the electrophoresis. Subsequently, oxone oxidation was carried out in order to obtain the expected saturated and unsaturated poly(ester-sulfone)s, and electrophoretic deposition (EPD) of the poly(ester-sulfone) onto stainless steel was performed. For unsaturated poly(ester-sulfone) onto stainless steel, subsequent UV irradiation cured the deposited film, improving the peeling strength of the coating.

    更新日期:2017-12-22
  • Enhanced self-assembly of block copolymers by surface modification of a guiding template
    Polym. J. (IF 2.145) Pub Date : 2017-12-19
    Woon Ik Park, Young Joong Choi, Jong Min Yuk, Hyeon Kook Seo, Kwang Ho Kim

    The formation of highly ordered patterns of block copolymers (BCPs) with high χ is important for next-generation lithography applications. We demonstrate here a surface-engineering methodology to enhance the self-assembly of poly(styrene-b-dimethylsiloxane) (PS-b-PDMS) BCPs with high χ by employing a hydroxyl-terminated polystyrene (PS-OH) brush. By precisely controlling the molecular weight (MW) and weight percent of PS-OH, well-ordered sub-20-nm BCP patterns were obtained over a large area in a short annealing time (<10 min) with the use of guiding templates. We systemically analyzed how the PS-OH brush affects the self-assembly kinetics of BCPs with various MWs and volume fractions. Moreover, the transmission electron microscopy (TEM) results strongly support that the PS-modulated surface plays an important role in the ordering of BCP patterns. We also achieved well-aligned 12 nm line and 18 nm dot patterns within 3 min by means of binary solvent vapor annealing at a moderate temperature under the optimum PS-OH brush conditions. These results provide a new platform for effective engineering and manipulation of the self-assembly of other BCPs for advanced BCP nanotechnologies.

    更新日期:2017-12-19
  • 3D structure of nano-oriented crystals of poly(ethylene terephthalate) formed by elongational crystallization from the melt
    Polym. J. (IF 2.145) Pub Date : 2017-12-14
    Kiyoka Okada, Yoshitaka Tanaka, Hiroyasu Masunaga, Masamichi Hikosaka

    We studied the elongational crystallization of poly(ethylene terephthalate) (PET) from the melt using polarizing optical microscope and X-ray observation. We verified that the structure and morphology discontinuously changed from conventional stacked lamellae of folded chain crystals (FCCs) to nano-oriented crystals (NOCs) when the elongational strain rate ( ε° ε ° ) exceeded a critical value of (ε°∗)≅102s−1 ( ε ° * ) ≅ 1 0 2 s - 1 . Therefore, the universality of NOC formation was verified. We found that the NOCs of PET show a novel three-dimensional (3D) structure and morphology: (i) nanocrystals (NCs) were arranged in a monoclinic lattice, which is a specific morphology for NOCs of PET, compared to iPP, and (ii) the unit cell structure of NOCs was a triclinic system with biaxial orientation. We showed the important role of the primary structure of the plate, such as a benzene ring, in the formation of a novel 3D structure and the morphology of the NOCs of PET. We also clarified that the NOCs of PET showed high performance, such as a high heat resistance temperature (Th) ≅ ≅ 281 °C, a high melting temperature (Tm) ≅ ≅ 285 °C, high maximum tensile stresses for the machine direction (MD) and transverse direction (TD) ≅ ≅ 2.8 × 102 and 74 MPa, respectively, and high Young’s moduli for MD and TD ≅ ≅ 5.4 and 1.7 GPa, respectively.

    更新日期:2017-12-14
  • Difference in dilute aqueous solution behavior between poly(ethylene glycol) and poly(ethylene oxide)
    Polym. J. (IF 2.145) Pub Date : 2017-12-14
    Akihisa Nakamura, Yutaka Aoki, Masashi Osa, Daichi Ida, Takenao Yoshizaki

    Static light scattering behavior was examined for poly(ethylene glycol) (PEG) and poly(ethylene oxide) (PEO) of small weight-average molecular weight Mw (3 × 103−2 × 104), in methanol and water at 25.0 °C, the former polymer having hydroxy groups at both ends and the latter having a methoxy group at one end and a hydroxy group at the other. It was found that some aggregates of large size are formed in aqueous solutions of the PEO samples with Mw = 3.81 × 103 and 7.00 × 103, while all PEG and PEO samples are isolated in methanol solutions, and the PEG samples and the PEO sample of the largest Mw (=1.60 × 104) are also isolated even in the aqueous solutions. From the results of dynamic light scattering measurements for the aqueous solution of the PEO sample with Mw = 3.81 × 103 at 25.0 °C, there were detected two classes of scatterers having different sizes, i.e., the isolated chains and aggregates, the apparent hydrodynamic radius of the latter being ca. twenty times as large as that of the former.

    更新日期:2017-12-14
  • 3D-polythiophene foam on a TiO2 nanotube array as a substrate for photogenerated Pt nanoparticles as an advanced catalyst for the oxygen reduction reaction
    Polym. J. (IF 2.145) Pub Date : 2017-12-14
    Rajashekar Badam, Raman Vedarajan, Noriyoshi Matsumi

    The development of novel substrates that possess high durability, strong anchoring to catalytic metal nanoparticles and low charge transfer resistance as well as that can replace conventional carbon is of great importance. To improve the durability and reduce the cost of various energy devices, new methodologies are necessary. Therefore, we report the preparation of a macroporous hybrid material containing polythiophene electropolymerized onto TiO2 nanotubes (TNT). The prepared foam-like hybrid material exhibited a very low charge transfer resistance and was further modified with novel and green photogenerated Pt nanoparticles. The material exhibited very strong metal substrate interactions, resulting in high durability during the oxygen reduction reaction (ORR). This study proposes a novel macroporous organic/inorganic hybrid material for use as an alternative material to replace conventional carbon substrates in ORR catalysts.

    更新日期:2017-12-14
  • Gas transport properties of polybenzoxazole–silica hybrid membranes prepared with different alkoxysilanes
    Polym. J. (IF 2.145) Pub Date : 2017-12-07
    Tomoyuki Suzuki, Yusuke Otsuki

    The gas transport properties of polybenzoxazole (PBO)–silica hybrid membranes were investigated. The PBO–silica hybrid membranes were prepared with poly(o-hydroxy amide) (PHA) as a precursor and various alkoxysilanes via thermal oxazolization and sol–gel processes. The thermal decomposition temperature of the hybrid membranes increased with increasing silica content, indicating that the thermal stability was improved by hybridization with silica. The gas permeabilities of the PBO–silica hybrid membranes also increased with increasing silica content and thermal treatment temperature. It is worth noting that the hybrid membranes prepared with tetraethoxysilane (TEOS) as the selected alkoxysilane showed simultaneous enhancements in CO2 permeability and CO2/CH4 selectivity with increasing silica content and thermal treatment temperature. The prominent CO2/CH4 separation ability of the PBO–silica hybrid membranes prepared with TEOS might be attributable to free volume holes created around the polymer/silica interfacial area and increased intermolecular chain distance, which improved size-selective CO2/CH4 separation.

    更新日期:2017-12-14
  • In pursuit of Moore’s Law: polymer chemistry in action
    Polym. J. (IF 2.145) Pub Date : 2017-11-01
    Hong Xu, Vasiliki Kosma, Emmanuel P Giannelis, Christopher K Ober

    In pursuit of Moore’s Law: polymer chemistry in action In pursuit of Moore’s Law: polymer chemistry in action, Published online: 01 November 2017; doi:10.1038/pj.2017.64 A focused review of photoresist strategies that have been studied over the past few decades driven by the demands of Moore’s law. Selected results are discussed with emphasis on the choice of photoresist chemistry depending on the particulars of each radiation type or patterning strategy, while we present special architectures of photoresists that have attracted a great interest in the semiconductor field.

    更新日期:2017-12-14
  • Antimicrobial cationic polymers: from structural design to functional control
    Polym. J. (IF 2.145) Pub Date : 2017-11-01
    Yuchong Yang, Zhengguo Cai, Zehuan Huang, Xiaoyan Tang, Xi Zhang

    Antimicrobial cationic polymers: from structural design to functional control Antimicrobial cationic polymers: from structural design to functional control, Published online: 01 November 2017; doi:10.1038/pj.2017.72 Antimicrobial cationic polymers mainly contain two functional components: the cationic groups and the hydrophobic groups. The antimicrobial activity is influenced by the type, amount, location and distribution of these two components. This review summarizes the structural designs of antimicrobial cationic polymers from primary to secondary structures, from covalent to noncovalent syntheses and from bulk to surface. It will provide some guidelines for developing molecular engineering of antimicrobial cationic polymers with tailor-made structures and functions.

    更新日期:2017-12-14
  • Diels–Alder polymerization: a versatile synthetic method toward functional polyphenylenes, ladder polymers and graphene nanoribbons
    Polym. J. (IF 2.145) Pub Date : 2017-11-01
    Ian Cheng-Yi Hou, Yunbin Hu, Akimitsu Narita, Klaus Müllen

    Diels–Alder polymerization: a versatile synthetic method toward functional polyphenylenes, ladder polymers and graphene nanoribbons Diels–Alder polymerization: a versatile synthetic method toward functional polyphenylenes, ladder polymers and graphene nanoribbons, Published online: 01 November 2017; doi:10.1038/pj.2017.69 In this review, we summarize the use of Diels–Alder reaction in the synthesis of arylene-based polymers, including polyphenylenes and ladder polymers, as well as graphene nanoribbons. These polymer materials are structurally related to each other, but rarely discussed all together in a same context. The importance and versatility of the Diels–Alder polymerization is highlighted for the synthesis of such polymers with various potential applications, for example, as polymer electrolyte membrane and organic semiconductors.

    更新日期:2017-12-14
  • Sequence-controlled polymers via reversible-deactivation radical polymerization
    Polym. J. (IF 2.145) Pub Date : 2017-10-25
    Makoto Ouchi, Mitsuo Sawamoto

    Sequence-controlled polymers via reversible-deactivation radical polymerization Sequence-controlled polymers via reversible-deactivation radical polymerization, Published online: 25 October 2017; doi:10.1038/pj.2017.66 The development of reversible-deactivation radical polymerization (RDRP) has made a great contribution not only to control of molecular weight and terminal structures but also to precise syntheses of copolymers. In particular, introducing a new concept into RDRP allows ‘sequence control’, which might lead to construction of ‘alphabet polymer’ bearing well-defined sequence like peptides in nature. Herein, some methodologies to realize sequence control based on RDRP are reviewed.

    更新日期:2017-12-14
  • Polymers for carrying and storing hydrogen
    Polym. J. (IF 2.145) Pub Date : 2017-10-25
    Ryo Kato, Hiroyuki Nishide

    Polymers for carrying and storing hydrogen Polymers for carrying and storing hydrogen, Published online: 25 October 2017; doi:10.1038/pj.2017.70 Organic polymers for hydrogen storage and their molecular design were reviewed. Porous organic polymers reversibly stored and released hydrogen through hydrogen physisorption on their highly porous structures. Polymers containing ketone or N-heterocycle groups fixed and stored hydrogen under atmospheric pressure through the formation of chemical bonds: the hydrogenated polymers released hydrogen in the presence of catalysts at mild conditions. The advantages of the polymers enable easy handling and provide portable hydrogen-carrying materials for use in, for example, a home/on-site or pocketable hydrogen-supply system.

    更新日期:2017-12-13
  • Polyion complex micelle formation from double-hydrophilic block copolymers composed of charged and non-charged segments in aqueous media
    Polym. J. (IF 2.145) Pub Date : 2017-10-25
    Atsushi Harada, Kazunori Kataoka

    Polyion complex micelle formation from double-hydrophilic block copolymers composed of charged and non-charged segments in aqueous media Polyion complex micelle formation from double-hydrophilic block copolymers composed of charged and non-charged segments in aqueous media, Published online: 25 October 2017; doi:10.1038/pj.2017.67 This review focuses on the physicochemical characterization of polyion complex (PIC) micelles, particularly addressing the critical molecular factors to determine the self-assembly scheme of double-hydrophilic block copolymers composed of charged and non-charged segments into micelle structures. The process of PIC micelle formation provides new insights on the block copolymer self-assembly in thermodynamically equilibrium condition in aqueous medium, such as chain length recognition and transition from uPIC, which is the PIC of smallest neutralizing unit, to PIC micelle structures.

    更新日期:2017-12-13
  • Topology-transformable polymers: linear–branched polymer structural transformation via the mechanical linking of polymer chains
    Polym. J. (IF 2.145) Pub Date : 2017-10-25
    Toshikazu Takata, Daisuke Aoki

    Topology-transformable polymers: linear–branched polymer structural transformation via the mechanical linking of polymer chains Topology-transformable polymers: linear–branched polymer structural transformation via the mechanical linking of polymer chains, Published online: 25 October 2017; doi:10.1038/pj.2017.60 Synthesis and dynamic nature of macromolecular systems having mechanically linked polymer chains, which can undertake the topology transformation, are described. The rotaxane linking of polymer chains plays a crucial role in these systems. Successful syntheses of macromolecular [2]rotaxane (M2R) possessing single polymer axle and one crown ether wheel made possible the development of topology-transformable polymers from star to linear. Furthermore, rotaxane-linked ABC triblock copolymer and 4-arm and 6-arm star polymers were also synthesized and transformed to other topological polymers along with the property change.

    更新日期:2017-12-13
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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