TABLE OF CONTENTS

Volume 42, Issue 1 (January 2010)

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Editorials

A new era of Polymer Journal: a message from the SPSJ President FREE

Mitsuo Sawamoto President

Polym J 42: 1; doi:10.1038/pj.2009.305

Enhancing Polymer Journal's international impact FREE

Toshikazu Takata Editor-in-Chief

Polym J 42: 2; doi:10.1038/pj.2009.327

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Review

Polymer Synthesis and Reactions

Synthesis and structure determination of helical polymers FREE

Eiji Yashima

Polym J 42: 3-16; doi:10.1038/pj.2009.314

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The recent remarkable progress in structural investigations of helical polymers by high-resolution atomic force microscopy provides their exact helical structures including helical pitch and handedness. Seeing is believing!

Subject Category: Polymer Synthesis and Reactions

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Invited Articles

Polymer Synthesis and Reactions

Carbonyl-phosphine hetero-ligated half-metallocene iron(II) catalysts for living radical polymerization: concomitant activity and stability FREE

Muneki Ishio, Takaya Terashima, Makoto Ouchi and Mitsuo Sawamoto

Polym J 42: 17-24; doi:10.1038/pj.2009.315

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Two neutral ligands, carbonyl and phosphine, were cooperatively incorporated into half-metallocene iron(II) complexes [CpFeBr(CO)(PR3)] for more active and versatile systems in transition metal-catalyzed living radical polymerization. Among the CpFeBr(CO)(PR3) complexes examined, CpFeBr(CO)(PMePh2) showed the highest activity and the best controllability, and the ‘living’ character of the polymerizations therewith was proved by sequential monomer-addition experiments. In spite of the high activity, the Fe(II) complex is stable and robust enough to be handled under air, rendering it suitable for practical use.

Subject Category: Polymer Synthesis and Reactions

Polymer Structures

Molecular dynamics and orientation of stretched rubber by solid-state 13C NMR FREE

Hideaki Kimura, Hidehiko Dohi, Marina Kotani, Takanobu Matsunaga, Kazuo Yamauchi, Hironori Kaji, Hiromichi Kurosu and Tetsuo Asakura

Polym J 42: 25-30; doi:10.1038/pj.2009.307

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The molecular dynamics and orientation of vulcanized natural rubber stretched at low extension ratio were studied by solid-state 13C NMR and density functional theory (DFT) calculations. Isoprene units of the oriented rubber chains in stretched NR rotate rapidly around an axis that almost aligned with C=C bond direction of polyisoprene.

Subject Category: Polymer Structures

Functional Polymers

Enantioseparation using amylose esters as chiral stationary phases for high-performance liquid chromatography FREE

Yuri Sugiura, Chiyo Yamamoto, Tomoyuki Ikai, Masami Kamigaito and Yoshio Okamoto

Polym J 42: 31-36; doi:10.1038/pj.2009.300

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Novel amylose ester derivatives were synthesized and their chiral recognition abilities as chiral stationary phases for high-performance liquid chromatography were evaluated. Among the prepared derivatives, the nonsubstituted cinnamate derivative showed a relatively high chiral recognition, and interestingly, its ability was influenced by the preparation conditions of packing materials using silica gel as a support.

Subject Category: Functional Polymers

Supramolecular Polymers

Quantum yield and morphology control of BODIPY-based supramolecular self-assembly with a chiral polymer inhibitor FREE

Atsushi Nagai, Kenta Kokado, Junpei Miyake and Yoshiki Chujo

Polym J 42: 37-42; doi:10.1038/pj.2009.302

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Chiral rod-coil type-organoboron polymers, S-poly and R-poly, have been prepared from Sonogashira coupling reaction of BODIPY-based monomer bearing bis-iodophenyl and decyl groups with S- or R-binaphthyl derivatives. The SEM analysis of each chiral polymer revealed μm-sized fiber-like structures formed by aggregation of each particle, however, the mixed polymer (S-poly/R-poly = 30/70) showed complete particle structures from nm to μm sizes, and the Φ F of the mixed polymer was significantly high (0.98).

Subject Category: Supramolecular Polymers

Self-assembled Materials

Synthesis of block copolymers consisting of poly(3-hexylthiophene) and polystyrene segments through ionic interaction and their self-assembly behavior FREE

Tomoya Higashihara, Ayumi Takahashi, Syuhei Tajima, Sangwoo Jin, Yecheol Rho, Moonhor Ree and Mitsuru Ueda

Polym J 42: 43-50; doi:10.1038/pj.2009.312

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Well-defined aniline-chain-end-functionalized regioregular poly(3–hexylthiophene)s (P3HT-NH2) have been synthesized on the basis of Grignard metathesis polymerization. The selectivity of monofunctionalization and the high degree of amine functionality (85–92%) were confirmed by MALDI-TOF mass spectroscopy. A block copolymer through ionic interaction was successfully synthesized simply by blending P3HT-NH2 with carboxy chain-end-functionalized polystyrene. Thermal and optical properties of the block copolymer are investigated by DSC, TGA and UV-vis spectroscopy. The self-assembly behavior of the polymer was observed by AFM showing nanofibril structures with 12–15 nm width.

Subject Category: Self-assembled Materials

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Original Articles

Polymer Synthesis and Reactions

Properties and curing kinetics of C21-based reactive polyamides as epoxy-curing agents derived from tung oil FREE

Kun Huang, Jianling Xia, Xiaohua Yang, Mei Li and Haiyang Ding

Polym J 42: 51-57; doi:10.1038/pj.2009.303

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Three C21-based reactive polyamides with various amine values as epoxy-curing agents were synthesized from tung oil and different polyamines. It was found that the cured materials were superior to those cured by widely used C36-based polyamides with regard to mechanical properties. The glass transition temperatures of three cured C21-based polyamides were found to be higher than that of C36-based polyamides. The curing kinetics were studied and nonisothermal DSC curves show a good agreement with theoretically calculated ones.

Subject Category: Polymer Synthesis and Reactions

Poly(methyl methacrylate) (PMMA)-based hybrid materials with reactive zirconium oxide nanocrystals FREE

Takeshi Otsuka, and Yoshiki Chujo

Polym J 42: 58-65; doi:10.1038/pj.2009.309

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Transparent and homogeneous hybrids were synthesized from poly(methyl methacrylate) (PMMA) and aqueous dispersed zirconium oxide nanocrystals (ZrO2-NCs) with a coupling agent, 3-(methacryloxy)propyltrimethoxysilane (MPTS). The covalent bonding between PMMA- and MPTS-modified ZrO2 nanocrystals is crucial to obtain nanoscale dispersed hybrid materials. The hybrid films retained good optical transparency compared with that of PMMA/ZrO2 blend composites and will be promisingly applied for optical functional materials and coatings.

Subject Category: Polymer Synthesis and Reactions

Effects of properties of the surface layer of seed particles on the formation of golf ball-like polymer particles by seeded dispersion polymerization  FREE

Natsumi Konishi, Teruhisa Fujibayashi, Takuya Tanaka, Hideto Minami and Masayoshi Okubo

Polym J 42: 66-71; doi:10.1038/pj.2009.313

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Micrometer-sized, monodisperse polystyrene (PS)/poly(styrene-cosodium styrene sulfonate) (P(S-NaSS))/poly(n-butyl methacrylate)(Pn-BMA) composite particles having a ‘golf ball-like’ shape were prepared by seeded dispersion polymerization of n-BMA with PS-core/P(S-NaSS)-shell seed particles in the presence of dodecane droplets. The effect of the P(S-NaSS)-shell properties of seed particles on the formation of golf ball-like particles was investigated. We clarified that golf ball-like particles could be obtained by proper selection of the hydrophilicity and molecular weight of the shell moiety.

Subject Category: Polymer Synthesis and Reactions

Polymer Structures

Direct condensation polymerization of N-alkylated p-aminobenzoic acid and packing of rigid-rod main chains with flexible side chains FREE

Yuji Shibasaki, Yoko Abe, Natsuki Sato, Atsuhiro Fujimori and Yoshiyuki Oishi

Polym J 42: 72-80; doi:10.1038/pj.2009.306

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Direct condensation polymerization of N-alkylated aminobenzoic acid was carried out using hexachloroethane, triphenylphosphine and pyridine as condensation reagents. Pale-yellow, fibrous polymers (PABAn, where n is the number of carbon atoms of the side chain) were obtained in 46–87% yields with an inherent viscosity of 0.30–1.18 per 100ml g−1 (sulfuric acid, 30 °C). DSC analysis and powder X-ray scattering of polymer samples indicated that PABAn with Me, Pr, Bu, Pe and Ste as side chains were crystalline polymers. X-ray scattering profiles indicated that PABAn with n=0, 3, 4 and 5 crystallized in an orthorhombic lattice, whereas PABA1 crystallized in a monoclinic lattice. PABA17 crystallized with hexagonal packing at the long side chain with an interplanar spacing of 4.2Å.

Subject Category: Polymer Structures

Physical Properties of Polymers

A two-dimensional IR correlation spectroscopic study of the conformational changes in syndiotactic polypropylene during crystallization FREE

Kai Zheng, Ruigang Liu and Yong Huang

Polym J 42: 81-85; doi:10.1038/pj.2009.304

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Conformational changes of sPP during melting and isothermal crystallization process were studied by IR and 2D-correlation analysis. The absorption intensity of the band at 963 cm−1 (amorphous) increases earlier than that of the band at 978 cm−1 (shorter helix), and that of the band at 867 and 812cm−1 (crystalline helix). We found that partial sPP chains in amorphous component change their conformation first and then adjust their local conformations into short helix, and then crystallization occurs.

Subject Category: Physical Properties of Polymers

Functional Polymers

Development of chemically amplified reaction development patterning FREE

Xu Cheng, Akio Takahashi and Toshiyuki Oyama

Polym J 42: 86-94; doi:10.1038/pj.2009.308

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Aromatic sulfonate esters as acid amplifiers were introduced into a photosensitive polyetherimide system on the basis of reaction development patterning (RDP), composed of polyetherimide and a diazonaphthoquinone (DNQ) as a photosensitive agent. The resulting chemically amplified RDP (CARDP) system enabled positive-tone pattern formation with a reduced amount of the photosensitive agent and exposure dose. In particular, the use of 2SCE resulted in the formation of clear patterns with 5wt% of the photosensitive agent with a sensitivity of 125mJ/cm2. The patterns prepared by CARDP showed good thermal properties.

Subject Category: Functional Polymers

Biopolymers, Bio-related Polymer Materials Polymer Engineering

Layer-by-layer fabrication of well-packed gold nanoparticle assemblies guided by a β-sheet peptide network FREE

Nobuyuki Higashi, Toshikazu Takagi and Tomoyuki Koga

Polym J 42: 95-99; doi:10.1038/pj.2009.311

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LbL multilayer properties such as thickness, conformation of the peptide component, homogeneity and periodicity of nanoparticle layers were significantly affected by the kind of polycations. The combination of anionic PLGA-coated gold nanoparticle and cationic PLL induced a β-sheet formation, which enables the fabrication of a homogeneously well-packed gold nanoparticle multilayer without aggregation.

Subject Category: Biopolymers, Bio-related Polymer Materials

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Rapid Communication

Spontaneous extrusion of porous amphiphilic triblock copolymeric microfibers under microfluidic conditions FREE

Mohana Marimuthu and Sanghyo Kim

Polym J 42: 100-102; doi:10.1038/pj.2009.301