2022/01/08 更新

写真a

キムラ クニオ
木村 邦生
KIMURA Kunio
所属
環境生命科学学域 教授
職名
教授
外部リンク

学位

  • 博士(工学) ( 大阪大学 )

研究キーワード

  • 高分子の高次構造形成

  • 精密重縮合法の開発

  • 高分子のアップサイクル

  • バイオマスからの高性能高分子合成

  • 新規高性能高分子の合成

研究分野

  • ナノテク・材料 / 高分子化学

学歴

  • 大阪大学    

    - 1983年

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    国名: 日本国

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  • 大阪大学   Graduate School, Division of Engineering  

    - 1983年

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  • 大阪大学   School of Engineering  

    - 1981年

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    国名: 日本国

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  • 大阪大学   Faculty of Engineering  

    - 1981年

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所属学協会

 

論文

  • Morphology and growth rate of spherulite of cyclic poly(ε-caprolactone) having a triazole group at the closing point 査読

    Atsushi Shinya, Ryogo Ono, Hironori Atarashi, Shinichi Yamazaki, Kunio Kimura

    Polymer   122660 - 122660   2020年5月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1016/j.polymer.2020.122660

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  • 倉敷帆布に関する意識調査とデザイン提案

    福村愛美, 津呂育孝, 木村邦生

    76 ( 4 )   134 - 143   2020年4月

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    担当区分:最終著者, 責任著者   掲載種別:研究論文(学術雑誌)  

    DOI: 10.2115/fiberst.2020-0015

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  • Molecular weight dependence of the growth rate of spherulite of cyclic poly(ε-caprolactone) polymerized by ring expansion reaction 査読

    Ryogo Ono, Hironori Atarashi, Shinichi Yamazaki, Kunio Kimura

    Polymer   194   122403 - 122403   2020年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1016/j.polymer.2020.122403

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  • Size control of aromatic polyamide hollow spheres prepared by reaction-induced phase separation 査読

    Hirofumi Nakayama, Naoto Adachi, Hironori Atarashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    POLYMER   111   239 - 243   2017年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Size control of the poly (1,4-phenylene-5-hydroxyisophthalamide) hollow spheres was examined by tuning the polymerization condition, focusing on concentration, temperature and solvent. Higher concentration lowered the diameter owing to the higher degree of super-saturation for nucleation. Temperature drop during the polymerization just before the nucleation was so effective to make the diameter smaller. Moreover, the diameter was susceptive to the solubility of oligomers in the solvent, and higher content of liquid paraffin in the aromatic solvent lowered the solubility, resulting in the decrease in the diameter. Based on these results, the combination of the temperature drop and the solvent effect was the most desirable to prepare the smallest hollow spheres, and the diameter of hollow spheres could be controlled from 4.4 to 0.7 mu m. (C) 2017 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2017.01.060

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  • Preparation of aromatic polyimide particles having clear morphology by polymerization of salt monomers 査読

    Daisaku Shojo, Hidekazu Sugimori, Shinichi Yamazaki, Kunio Kimura

    HIGH PERFORMANCE POLYMERS   28 ( 10 )   1139 - 1150   2016年12月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SAGE PUBLICATIONS LTD  

    Crystals of salt monomer prepared from aromatic tetracarboxylic acids and aromatic diamines were polymerized at 220 degrees C for 3 h and at 400 degrees C for 3 h under argon flow. Highly crystalline polyimide particles having clear morphology were obtained with good yield. They were lozenge-like crystals, long plate-like crystals, fibrillar crystals, and spherical aggregates of plate-like crystals. The crystals of salt monomer were polymerized in the solid-state with maintaining the morphology, and therefore the morphology of the polyimide particles were the same to that of the crystals of the corresponding salt monomer. Molecular orientation in the lozenge-shaped crystal of poly(p-phenylene pyromelliteimide) was examined by selected area electron diffraction, and the polymer molecules aligned perpendicular to the plate plane which was the direction of the thickness. Obtained particles possessed good thermal stability.

    DOI: 10.1177/0954008315619998

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  • Preparation of poly(ether ketone)s derived from 2,5-furandicarboxylic acid via nucleophilic aromatic substitution polymerization 査読

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   54 ( 19 )   3094 - 3101   2016年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    From the viewpoint of the suppression of the petroleum consumption, aromatic poly(ether ketone)s (PEKs) were prepared by the nucleophilic aromatic substitution polymerization of 2,5-bis(4-fluorobenzoyl)furan (BFBF) synthesized from biomass and aromatic bisphenols. The model reaction of BFBF and p-methoxyphenol revealed that BFBF possessed enough reactivity for the nucleophilic aromatic substitution reactions. The polymerizations of BFBF and aromatic bisphenols afforded high molecular weight polymers with good yields in N-methylpyrrolidone and diphenyl sulfone for several hours. The longer polymerization time brought about the formation of insoluble parts in any solvents and reduction of molecular weight. The obtained PEKs were thermoplastics and exhibited good thermal stability, mechanical properties, and chemical resistance comparable to common high-performance polymers. The thermal properties were tunable with the structure of bisphenols. (c) 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 3094-3101

    DOI: 10.1002/pola.28193

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  • Preparation of helical crystals of aromatic poly(ester-imide) and on-off switching of helix formation 査読

    Takuya Ohnishi, Miki Nakagawa, Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    POLYMER   98   378 - 386   2016年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Preparation of poly[4-(5-oxy-1,3-dioxoisoindoline-2-yl)benzoyl] (PODB) crystals, which was an intractable aromatic poly(ester-imide), was examined by means of reaction-induced crystallization of oligomers during the polymerization. Highly crystalline PODB helical ribbons were obtained by the polymerization of N-(4-carboxyphenyl)-4-acetoxyphthalimide in aromatic solvent at 280-330 degrees C at a concentration of 0.5-1.0%. The PODB molecules aligned along the long axis of the helical ribbon. The pitch of the helix increased with the polymerization temperature and it could be controlled from 320 nm to 1.3 mu m. Further, the fibrillar PODB crystals comprised of the helical and the non-helical blocks were prepared by the on-off switching of the helical morphology with the changing the temperature and the concentration of the polymerization. These results provided the methodology for the morphology control of polymer crystals. (C) 2016 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2016.06.055

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  • One-Pot Preparation of Aromatic Poly(ester-imide) Crystals by Crystallization during Polymerization 査読

    Takuya Ohnishi, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF FIBER SCIENCE AND TECHNOLOGY   72 ( 2 )   49 - 53   2016年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SOC FIBER SCIENCE TECHNOLOGY  

    One-pot preparation of poly[ 4-(5-oxy-1,3-dioxoisoindolin-2-yl) benzoyl] (PODB) crystals which was an aromatic poly(ester-imide) was examined by means of the reaction-induced crystallization during polymerization of 4-acetoxyphthalic anhydride (APA) and 4-aminobenzoic acid (AmBA). Two-step heating program was suitable for the formation of PODB crystals. The reaction of APA and AmBA at 150 degrees C, which was much lower than the polymerization temperature, was of importance to synthesize N-(4-carboxyphenyl)-4-acetoxyphthalimide. Even though the amide moiety was incorporated, the PODB crystals were formed as precipitates by heating at 150 degrees C and then at 280-350 degrees C. Morphology of PODB depended on the polymerization conditions and fibrillar crystals, rod-like crystals and ribbon-like crystals were obtained. This result provided a novel one-pot procedure for the control of the PODB morphology.

    DOI: 10.2115/fiberst.2016-0008

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  • Preparation of Poly(ether ketone)s Derived from 2,5-Furandicarboxylic Acid by Polymerization in Ionic Liquid 査読

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

    MACROMOLECULES   49 ( 4 )   1252 - 1258   2016年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:AMER CHEMICAL SOC  

    Aromatic poly(ether ketone)s were synthesized by the Friedel Crafts polymerization of 2,5-furandicarbonyl dichloride prepared from biomass and petroleum-based aromatic ethers such as diphenyl ether and 1,4-diphenoxybenzene with aluminum chloride (AlCl3). The polymerizations in common molecular solvents such as 1,2-dichloroethane and nitrobenzene did not afford polymers. The Friedel-Crafts polymerization usually undergoes in the swollen gel of the oligomer-AlCl3 complexes; the precipitated physical gels had not been enough swollen. The polymerizations were carried out in various ionic liquids to form swollen gels. The polymerizations proceeded in specific ionic liquid such as 1-butyl-3-methylimidazolium chloride ([C(4)min] CO, and high molecular weight polymers were obtained with good yield. The gels formed in [C(4)mim] Cl were more highly swollen, and additionally the rate constant estimated by the model reaction of 2,5-furandicarbonyl dichloride and anisole was higher in [C4(m)im]Cl than that in 1,2-dichloroethane. The obtained poly(ether ketone)s exhibited good thermal stability and chemical resistance comparable to common poly(ether ketone)s.

    DOI: 10.1021/acs.macromol.5b02788

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  • High Performance Polyesters Prepared from Bio-Based 2,5-Furandicarboxylic Acid 査読

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF FIBER SCIENCE AND TECHNOLOGY   72 ( 2 )   54 - 60   2016年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SOC FIBER SCIENCE TECHNOLOGY  

    Aromatic polyesters were synthesized by the polymerization of bio-based 2,5-furandicarboxylic acid (FDCA) with petroleum-based 1,3-and 1,4-diacetoxybenzene (DAB) from the viewpoint of the suppression of the petroleum consumption to develop the sustainable development society. Polyesters prepared at the molar ratio of 1,4-DAB in DAB (chi) of less than 60 mol% showed meltability under decomposition temperature. When the value of chi was 20-60 mol%, the polyesters exhibited optical anisotropicity in melt phase, suggesting the thermotropic liquid crystallinity. The phase transition temperature of these polyesters depended on the composition and it was tunable by the. value. The film of the polyesters prepared at. of 20 mol% possessed 1.2 GPa of the modulus, 26.0 MPa and 2.9% of the strength and elongation at break, respectively. Polyesters based on FDCA possessed good thermal stability and mechanical properties comparable to common aromatic polyesters.

    DOI: 10.2115/fiberst.2016-0009

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  • Synthesis of Poly(ether ketone)s from 2,5-Thiophenedicarboxylic Acid 査読

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY   29 ( 2 )   243 - 246   2016年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:TECHNICAL ASSOC PHOTOPOLYMERS,JAPAN  

    The Friedel-Crafts polymerization of 2,5-thiophenedicarbonyl dichloride and diphenyl ether in 1,2-dichloroethane afforded only low molecular weight of poly(ether ketone) containing thiophene-ring. In contrast to this, the polymerization in 1-butyl-3-methylimidazolium chloride-aluminum chloride mixture gave high molecular weight polymers. The polymerizations in ionic liquids were a new approach to expand possibility of polymer synthesis such as preparation of polymer containing heterocyclic rings. The obtained poly(ether ketone) exhibited good thermal stability and chemical resistance comparable to common poly(ether ketone)s.

    DOI: 10.2494/photopolymer.29.243

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  • Preparation of poly(ester-imide) ribbons comprised of helical and non-helical blocks by copolymerization 査読

    T. Ohnishi, T. Uchida, S. Yamazaki, K. Kimura

    RSC ADVANCES   6 ( 104 )   101995 - 102002   2016年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

    Helical ribbons of poly[4-(5-oxy-1,3-dioxoisoindoline-2-yl) benzoyl] (PODB) were previously prepared by the homo-polymerization of N-(4-carboxyphenyl)-4-acetoxyphthalimide (CAP) in aromatic solvents. The copolymerization of CAP and p-acetoxybenzoic acid (ABA) was examined to change the helical morphology. The helical morphology was extinguished by the copolymerization of a small amount of ABA at 280 degrees C at a concentration of 1.0% in aromatic solvent. Based on these results, ABA was added stepwise during the homo-polymerization of CAP. When a small amount of ABA was added, copolymer crystals comprised of helical and non-helical blocks were formed. The non-helical blocks grew on the PODB helical ribbons by the precipitation of co-oligomers. This result provides a novel method to control helical morphology by copolymerization.

    DOI: 10.1039/c6ra22494f

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  • Consideration on formation mechanism of aromatic polyamide hollow spheres prepared by reaction-Induced phase separation 査読

    Hirofumi Nakayama, Yuji Fujitsu, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    J. Polym. Sci., Part A: Polym. Chem.   53 ( 17 )   1966 - 1974   2015年

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    記述言語:英語  

    DOI: 10.1002/pola.27683

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  • Preparation of aromatic polyesters by direct polymerization in the presence of boronic anhydride under non-stoichiometric condition 査読

    Masahiro Kihara, Yuma Sakakiyama, Shinichi Yamazaki, Kunio Kimura

    Polymer   66   222 - 229   2015年

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    記述言語:英語  

    DOI: 10.1016/j.polymer.2015.04.019

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  • Hydrothermal synthesis of aromatic polyimide particles by using reaction-induced crystallization 査読

    Daisaku Shojo, Shinichi Yamazaki, Kunio Kimura

    J. Polym. Sci., Part A, Polym. Chem.   53 ( 24 )   2795 - 2799   2015年

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    記述言語:英語  

    DOI: 10.1002/pola.27791

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  • 多重水素結合性官能基を末端に有するポリエチレンおよびポリジオキサノンの結晶化 査読

    内村 美香, 岡崎 康平, 山崎 慎一, 木村 邦生

    高分子論文集   71 ( 11 )   562 - 572   2014年

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1295/koron.71.562

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  • Hollow Spheres of Aromatic Polyamide Prepared by Reaction-Induced Phase Separation 査読

    Yuji Fujitsu, Hirofumi Nakayama, Shinichi Yamazaki, Kunio Kimura

    J. Polym. Sci., Part A, Polym. Chem.   51 ( 4 )   780 - 785   2013年

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    記述言語:英語  

    DOI: 10.1002/pola.26467

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  • Preparation of Novel Naphthalene Polyimide and Its Morphology 査読

    Takashi Sawai, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    J. Photopolym. Sci. Technol.   26 ( 3 )   341 - 344   2013年

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    記述言語:英語  

    DOI: 10.2494/photopolymer.26.341

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  • Heterogeneous Polycondensation for Composition Control of Poly(p-mercaptobenzoyl-co-p-benzamide) by Shearing 査読

    Toshimitsu Ichimori, Shinichi Yamazaki, Kunio Kimura

    J. Polym. Sci., Part A, Polym. Chem.   51 ( 20 )   4301 - 4308   2013年

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    記述言語:英語  

    DOI: 10.1002/pola.26839

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  • Synthesis and morphology control of self-condensable naphthalene-containing polyimide by using reaction-induced crystallization 査読

    Takashi Sawai, Kanji Wakabayashi, Shinichi Yamazaki, Tetsuya Uchida, Yoshimitsu Sakaguchi, Kunio Kimura

    European Polymer Journal   49 ( 8 )   2334 - 2343   2013年

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    記述言語:英語  

    DOI: 10.1016/j.eurpolymj.2013.05.021

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  • Morphological Diversity and Nanofiber Networks of Poly(p-oxybenzoyl) Generated by Phase Separation During Copolymerization 査読

    Toshimitsu Ichimori, Kenta Mizuma, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    J. Appl. Polym. Sci.   128 ( 2 )   1282 - 1290   2013年

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    記述言語:英語  

    DOI: 10.1002/app.38554

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  • Morphosynthesis of poly(ether ketone) by reaction-induced crystallization during polymerization 査読

    Kanji Wakabayashi, Naofumi Sumi, Shinichi Yamazaki, Tetsuya Uchida, Kunio Kimura

    EUROPEAN POLYMER JOURNAL   48 ( 10 )   1787 - 1795   2012年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:PERGAMON-ELSEVIER SCIENCE LTD  

    Morphology control of poly(ether ketone) (PEK) was examined by using the crystallization during the nucleophilic aromatic substitution reaction of potassium salt of 4-fluoro-4'-hydroxybenzophenone. Polymerizations were carried out at 290 degrees C. The PEK was obtained as precipitates and its morphology was highly influenced by the polymerization condition such as the solvent, the concentration and the polymerization time. High crystalline spindle-like crystals were obtained by the polymerization in diphenyl sulfone (DPS) at a concentration of 5.0% for 2 h with the yield of 86%. The average length and width were 1.4 mu m and 300 nm respectively, and the maximum thickness was 130 nm. The surface was not smooth and it was hilly. The spindle-like crystal was likely consisted of multilayered lamellae comprised of the microcrystallites. The molecules were oriented perpendicular to the lamella. The polymerization in DPS at a higher concentration of 10.0% afforded the networks of nanofibres, of which the diameter was 100-250 nm. The obtained PEK precipitates possessed excellent thermal properties. (C) 2012 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.eurpolymj.2012.07.004

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  • Polymer electrolyte membranes derived from novel fluorine-containing poly(arylene ether ketone)s by controlled post-sulfonation 査読

    Yoshimitsu Sakaguchi, Atsushi Kaji, Kota Kitamura, Satoshi Takase, Kazushi Omote, Yoshinobu Asako, Kunio Kimura

    Polymer (United Kingdom)   53 ( 20 )   4388 - 4398   2012年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    Precise assignment with 1H, 13C and some two dimensional NMR measurements showed that sulfonation reaction by concentrated sulfuric acid at 30 °C of fluorine-containing poly(arylene ether ketone) copolymers derived from 4,4′-bis(2,4,5,6-pentafluorobenzoyl)diphenyl ether (BPDE) and 9,9-bis(4-hydroxypehnyl)fluorene (HF) and 2,2-bis(4-hydroxyphenyl)- 1,1,1,3,3,3-hexafluoropropane (6FBA) yielded quantitative introduction of sulfonic groups onto 2- and 7-positions of fluorene ring in HF unit. A series of sulfonated poly(arylene ether ketone)s with different ion exchange capacity was prepared by using this method with different compositions of HF and 6FBA, and membranes obtained from these polymers were characterized by TGA, moisture and water uptake, proton conductivity, methanol permeability, and Fenton testing. These membranes showed sufficient thermal stability, high proton conductivity at high humidified condition for PEFC and good balance in proton conductivity in water and methanol permeability for DMFC. On the other hand, they showed relatively high swelling by water probably due to weak intermolecular interaction caused by the existence of fluorine atoms in the polymer structure. © 2012 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2012.08.006

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  • Morphosynthesis of poly[4-(1,4-phenylene)oxyphthalimide] and copolymers prepared by reaction-induced crystallization during polymerization 査読

    Takashi Sawai, Kanji Wakabayashi, Shinichi Yamazaki, Tetsuya Uchida, Kunio Kimura

    JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS   50 ( 18 )   1293 - 1303   2012年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    Morphosynthesis of poly[4-(1,4-phenylene)oxyphthalimide] (POPI) and poly[4-(1,4-phenylene)oxyphthalimide-co-4-phthalimide] (POPI-PPI) was examined by using the crystallization during the polymerization. The POPI fibrillar crystals were obtained as precipitates with the formation of spherical aggregates of plate-like crystals. Some of the POPI fibrillar crystals were longer than 15 mu m. They possessed high crystallinity and the molecules aligned perpendicular to the long direction of the fibers. On the other hand, one-dimensional structures of POPI-PPI such as ribbon, cone, rod, and fiber were obtained as precipitates by the copolymerization. The copolymer molecules might align along the long direction of the cone-like crystals. The morphology of these poly(ether-imide)s could be controlled by not only the polymerization condition but also with the aid of copolymerization. (c) 2012 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2012

    DOI: 10.1002/polb.23122

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  • Characterization of hybrid composite membrane based polymer/precursor/ SiO 2 査読

    Uma Thanganathan, Yuta Nishina, Kunio Kimura, Satoshi Hayakawa, Rambabu Bobba

    Materials Letters   81   88 - 91   2012年8月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    New class of hybrid composite was synthesized via sol-gel process with the combination of poly(vinyl alcohol) (PVA), TEOS, 3- glycidyloxypropyltrimethoxysilane (GPTMS) reacted with the cross-linking agent glutaraldehyde. The composites demonstrated a maximum high proton conductivity of 1.7 × 10 - 2 S cm -1 at 140 °C and a relative humidity of 50% RH. The swelling ratio was calculated in dry and wet conditions, and the composites were found capable of swelling. The structural formation of the composites was studied by techniques such as FTIR, TGA and impedance spectroscopy, and it was concluded that these PVA-SiO 2/GPTMS/GA composite membranes exhibited excellent thermal, mechanical and conductivity properties. © 2012 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.matlet.2012.04.023

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  • Synthesis of organic/inorganic hybrid composite membranes and their structural and conductivity properties 査読

    Uma Thanganathan, Suresh Kumar, Akira Kishimoto, Kunio Kimura

    Materials Letters   72   81 - 87   2012年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    The present article describes the use of a less expensive non-perfluorinated polymer (polyvinyl alcohol, PVA), heteropolyacid (HPA), glutaraldehyde and 3-aminopropyltriethoxysilane (APTES) for the formation of high proton-conducting hybrid composite membranes. The conductivity of the PVA/PMA/Gl/APTES hybrid composite membranes was measured under varying conditions of temperature (from - 20 °C to 140 °C) and relative humidity (from 30 to 90%). Conductivity values in the range of 10 - 3-10 - 1 S cm - 1 were obtained for the hybrid membranes. These free-standing flexible films were mechanically stable and the corresponding composite membranes were thermally stable up to 300 °C. Their swelling ratio was calculated for dry and wet conditions at room temperature. © 2011 Elsevier B.V. All rights reserved.

    DOI: 10.1016/j.matlet.2011.12.066

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  • Selective Synthesis of Poly(p-oxybenzoyl) by Fractional Polycondensation: Enhancement of Selectivity by Shearing 査読

    Toshimitsu Ichimori, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   49 ( 21 )   4613 - 4617   2011年11月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    The influence of shear flow, especially the timing for the application of shearing, was examined to enhance the selectivity for the preparation of poly(p-oxybenzoyl) (Pp-OB) by using hydrodynamically induced phase separation during polymerization of 4-(4-acetoxybenzoyloxy) benzoic acid (p-ABAD) and m-acetoxybenzoic acid (m-ABA). The polymers containing few m-oxybenzoyl (m-OB) moieties were obtained as precipitates even at high content of m-OB moiety in feed (chi(f)) under shear flow. The content of m-OB moiety in the precipitates (chi(p)) prepared under shearing throughout the polymerization at the shear rate (gamma) of 489 s(-1) was 6.3 mol % even at chi(f) of 60 mol %. Especially, the Pp-OB was obtained as the precipitates at chi(f) of less than 50 mol %. The timing of the application of the shearing influenced the selectivity significantly, and the shearing just after the precipitation of the oligomers started was quite efficient to enhance the selectivity more. The chi(p) of the precipitates prepared with shearing at gamma of 489 s(-1) just after the precipitation was only 3.9 mol % even at chi(f) of 60 mol %. The shear flow reduced the difference in the reactivity between p-ABAD and m-ABA, resulting in the decrease in the selectivity with regard to the formation of p-oxybenzoyl homo-oligomer. However, the shear flow enhanced the difference in the miscibility between homo-oligomers and co-oligomers. This change in the miscibility by shear flow brought about the more rapid precipitation of homo-oligomers, leading to the enhancement of the selectivity. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 4613-4617, 2011

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  • Effects of topological constraint and knot entanglement on the crystal growth of polymers proved by growth rate of spherulite of cyclic polyethylene 査読

    Tsunaki Kitahara, Shinichi Yamazaki, Kunio Kimura

    Kobunshi Ronbunshu   68 ( 10 )   694 - 701   2011年10月

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)  

    In order to clarity tne effects ot entanglement species on nucleation ot polymers, we stuaiea tne growtn rate ot spneruute G of cyclic ana linear polyethylenes (C-PE and L-PE) from the melt as a function of degree of supercooling A T by means of polarizing optical microscope. We prepared several C-PEs with different weight average molecular weights M w=9300, 43600 and 86500, and L-PE with A/,=44000. G of all the sample were obeyed the equation, G = G 0 exp (-B/△T).BoîC-PE gradually increased with increasingM w. B is proportional to the surface free energy of the end surface of the nucleus, and this indicates that the regularity of folding surface increased with increasing M w. We consider that topological constraint of cyclic polymer becomes large with decreasing M., of the cyclic polymer. On the other hand, for C-PE and L-PE having almost the same M w (=44 k), G 0 of C-PE is much less than that of L-PE. Due to the topological constraint of cyclic polymer, we speculated that the adsorption mode on the crystal surface of C-PE is different than that of L-PE. ©2011, The Society of Polymer Science, Japan.

    DOI: 10.1295/koron.68.694

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  • Morphology Control of Various Aromatic Polyimidazoles-Preparation of Nanofibers 査読

    Jin Gong, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF APPLIED POLYMER SCIENCE   121 ( 5 )   2851 - 2860   2011年9月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    Morphology of four kinds of aromatic polyimidazoles was examined by using reaction-induced crystallization during solution polymerization at a concentration of 1% at 350 degrees C in liquid paraffin (LPF), dibenzyltoluene (DBT), and the mixture of these solvents. Aggregates of ribbon-like crystals of poly[2,6-(2,6-naphthalene)-benzobisimidazole] were obtained in LPF, and those of plate-like crystals were obtained in DBT/LPF-50 and in DBT. In contrast to this, the network structures of poly[2,2'-(2,6-naphthalene)-5,5'-bibenzimidazole)] (PNT-BBI) nanofibers with the diameter of 25 to 90 nm was mainly obtained in DBT. The network structures of the PNT-BBI nanofibers could be recognized as nonwoven fabrics of the high-performance polymers. Imidazole trimers were precipitated to form the ribbon-like crystals and then they were continuously supplied from solution to grow the crystals. Molecular weight increased by the polymerization on the surface of the crystals when they crystallized and in the crystals. The initially formed aggregates of ribbon-like crystals changed to the nanofibers with time. In the case of poly[2,6-(4,4'-biphenylene)-benzobisimidazole] and poly[2,2'-(4,4'-biphenylene)-5,5'-bibenzimidazole)], they exhibited various morphologies such as spheres, lath-like crystals, and the spherical aggregates of lath-like crystals depending on the solvent, but fibers like PNT-BBI were not formed. The crystals obtained in this study possessed very high crystallinity and the outstanding thermal stability measured by TGA. (C) 2011 Wiley Periodicals, Inc. J Appl Polym Sci 121: 2851-2860, 2011

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  • Preparation of Poly(p-oxybenzoyl) Crystals Using Direct Polymerization of p-Hydroxybenzoic Acid in the Presence of Boronic Anhydrides 査読

    Masahiro Kihara, Shin-Ichiro Kohama, Shota Umezono, Kanji Wakabayashi, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   49 ( 5 )   1088 - 1096   2011年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

    Poly(p-oxybenzoyl) (POB) crystals were prepared by reaction-induced crystallization during direct polymerization of p-hydroxybenzoic acid in the presence of boronic anhydrides. Polymerizations were carried out at 300 degrees C in dibenzyltoluene at a concentration of 1% with three kinds of anhydrides of boronic acid such as 3,4,5-trifluorophenylboronic acid (TFB), 4-methoxyphenylboronic acid (MPB) and 4-biphenylboronic acid (BPB). The POB crystals were formed as precipitates in the solution and the morphology was considerably influenced by both the structure of the boronic anhydride and its concentration (C(B)). Needle-like crystals were firmed in the presence of TFB anhydride (TFBA) at C(B)S of 5 and 10 mol % by the spiral growth of lamellae. Spherical aggregates of slab-like crystals were formed at C(B)S from 50 to 100 mol %. The polymerization with MPB anhydride and BPB anhydride (BPBA) also yielded the needle-like crystals at C(B)S of 50 and 5 mol %, respectively. The polymerization with TFBA at lower C(B) was favorable to prepare the needle-like crystal. Molecular weight was also influenced by the structure of the boronic anhydride and C(B). M(n) increased generally with C(B) and BPBA gave the highest M(n) of 14.7 x 10(3) at C(B) of 100 mol %. The loose packing of the molecules in the crystal caused by the bulkiness of the end-groups made the polymerization in the crystals more efficiently. Morphology and molecular weight of the POB crystals could be controlled by the chemical structure and the content of boronic anhydride. (C) 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 1088-1096, 2011

    DOI: 10.1002/pola.24521

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  • Micro-flowers of poly(p-phenylene pyromelliteimide) crystals 査読

    Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    POLYMER   52 ( 3 )   837 - 843   2011年2月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Morphology control of poly(p-phenylene pyromelliteimide) (PPPI) crystals was examined using reaction-induced crystallization of oligomers during solution polymerization of self-polymerizable N-(4'-aminophenyl)-3-carboxyl-4-alkoxycarbonylPhthalimide. Micro-flowers of the PPP1 needle-like crystals were formed in which the needle-like crystals grew radially from the center part as petals. The molecules aligned regularly along the long axis of the needle-like crystal. The structure of alkoxy group in the monomer and the monomer concentration influenced the size of the needle-like crystals, and their average length and width were changeable from 640 nm to 1.69 mu m and from 110 nm to 210 nm, respectively. The average thickness was 20 nm. The obtained micro-flowers possessed high crystallinity and exhibited excellent thermal stability. (C) 2010 Elsevier Ltd. All rights reserved.

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  • Preparation of Poly(p-phenylenepyromelliteimide) Microspheres with Rugged Surfaces Using Crystallization During Isothermal Polymerization 査読

    Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    MACROMOLECULAR CHEMISTRY AND PHYSICS   212 ( 2 )   159 - 167   2011年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

    Preparation of discrete PPPI microspheres was examined using the crystallization of oligomers during isothermal polymerization of PMDA and p-phenylene diisocyanate, and that of pyromellitic dithioanhydride and PPDA in poor solvents. In contrast to PPPI microspheres with smooth surfaces that were previously prepared by phase-separation during the polymerization of PPDA and PMDA, the microspheres obtained here consisted of flake-like lamellae with rugged surfaces. The diameters of the microspheres ranged from 0.5 to 6.7 mu m. They exhibited excellent thermal stability depending on the monomers. These results provide a new preparative procedure of the PPPI microsphere with a rugged surface.

    DOI: 10.1002/macp.201000510

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  • One-Pot Preparation of Aromatic Poly(azomethine ester) Fibrillar Crystals Using Reaction-Induced Crystallization 査読

    Jin Gong, Yasuhide Yakushi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   49 ( 1 )   127 - 137   2011年1月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL PUBLISHING, INC  

    Polymerizations of 4-(4-acetoxybenzylideneamino)-benzoic acid were performed in dibenzyltoluene (DBT) and a mixture of DBT and liquid paraffin at 350 degrees C for 6 h. Fibrillar crystals of poly[4-(4-oxybenzylideneamino)benzoyl] (POAB) having the width of 50-450 nm and the length of over 15 pm were obtained by the crystallization during the polymerization. The fibrillar crystals possessed high crystallinity and the molecular chains aligned perpendicular to the long axis of the fibrillar crystals. Plate-like crystals were initially formed by the crystallization of oligomers, and then they changed to the fibrillar crystals via the formation of bundle-like crystals after 1 h. Molecular weight increased by the further polymerization in the crystals. Based on these results, one-pot preparation of the fibrillar POAB crystals was examined by the polymerization of 4-acetoxybenzaldehyde and 4-aminobenzoic acid. The polymerization at 180 degrees C for 2 h and then at 350 degrees C for 6 h afforded the fibrillar crystals with a small amount of the ribbon-like crystals. Although the side-reaction to generate the p-benzamide sequences was not completely depressed, the sequence of heating in which 180 degrees C for the formation of the azomethine linkage and then 350 degrees C for the formation of the ester linkage was preferable to prepare the fibrillar POAB crystals. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 127-137, 2011

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  • Preparation of poly(2-oxy-6-naphthoyl) and copolymers using reaction-induced phase separation during direct polymerization in the presence of boronic anhydride 査読

    Masahiro Kihara, Shinichi Yamazaki, Kunio Kimura

    POLYMER CHEMISTRY   2 ( 5 )   1195 - 1202   2011年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

    Poly(2-oxy-6-naphthoyl) (PON) was obtained as precipitates by direct polymerization of 2-hydroxy-6-naphthoic acid (HNA) in the presence of boronic anhydrides such as 2,4,6-tris(3,4,5-trifluorophenyl)-1,3,5,2,4,6-trioxatriborinane (TFBA) and 2,4,6-tri(biphenyl-4-yl)-1,3,5,2,4,6-trioxatriborinane (BPBA). The polymerizations were carried out in an aromatic solvent at 300 degrees C for 24 h. Both morphology and molecular weight of the PON precipitates were considerably influenced by not only the structure of the boronic anhydride but also its concentration (c(B)). Spheres with needles on their surface were formed in the polymerization with TFBA at c(B) of 50-70 mol%, and those having smooth surface were obtained at c(B) of 100 mol%. The M(n) increased with the value of c(B) in the range from 2.7 x 10(3) to 9.0 x 10(3). Aggregates of cone-like crystals were prepared in the polymerization with BPBA at c(B) of 10-30 mol%, and spheres having rugged surface were formed at c(B) of 50-100 mol%. The M(n) also increased with the value of c(B) in the range from 5.4 x 10(3) to 12.9 x 10(3). These PON precipitates possessed high crystallinity in spite of the morphology. The copolymerization of HNA and 4-hydroxybenzoic acid (HBA) was also examined in the presence of BPBA at c(B) of 100 mol% with varying the content of HBA in feed (r(f)). Copolymers were obtained as spheres of which the content of 4-oxybenzoyl moiety was lower than the value of r(f) due to the difference in the solubility of the oligomers.

    DOI: 10.1039/c0py00420k

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  • Poly(2,5-benzimidazole) Nanofibers Prepared by Reaction-induced Crystyallization 査読

    Kazuya Kimura, Jin Gong, Shin-ichiro Kohama, Shinichi Yamazaki, Tetsuya Uchida, Kunio Kimura

    Polymer Journal   42 ( 5 )   375 - 382   2010年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    DOI: 10.1038/pj.2010.20

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  • Thermally Induced Solid-State Synthesis of Fluorine-Containing Poly(ether oxadiazole) 査読

    Yuka Maruyama, Yukihiko Maeda, Kanji Wakabayashi, Shinichi Yamazaki, Kunio Kimura

    J. Appl. Polym. Sci.   118 ( 1 )   91 - 98   2010年

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    記述言語:英語  

    DOI: 10.1002/app.32391

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  • Poly[2,6-(1,4-phenylene)-benzobisimidazole] Nanofiber Networks 査読

    Jin Gong, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    Macromolecular Chemistry and Physics   211 ( 20 )   2226 - 2232   2010年

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    記述言語:英語  

    DOI: 10.1002/macp.201000306

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  • 球晶成長速度をプローブにした脂肪族ポリエステル類のエステル交換反応を介した絡み合い解消の可能性の検証 査読

    山崎 慎一, 岡 卓也, 木村 邦生

    高分子論文集   66 ( 10 )   475 - 482   2009年

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    記述言語:日本語  

    DOI: 10.1295/koron.66.475

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  • Direct Synthesis of Wholly Aromatic Polyamides by Using Reaction-Induced Crystallization 査読

    Kazufumi Kobashi, Kentaro Kobayashi, Haruki Yasuda, Kentaro Arimachi, Testuya Uchida, Kanji Wakabayashi, Shinichi Yamazaki, Kunio Kimura

    Macromolecules   42 ( 16 )   6128 - 6135   2009年

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    記述言語:英語  

    DOI: 10.1021/ma9009033

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  • Formation and Morphology of “Shish-like” Fibril Crystals of Aliphatic Polyesters from the Sheared Melt 査読

    Shinichi Yamazaki, Manabu Itoh, Takuya Oka, Kunio Kimura

    European Polymer Journal   46 ( 1 )   58 - 68   2009年

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    記述言語:英語  

    DOI: 10.1016/j.eurpolymj.2009.09.003

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  • Improvement of adhesion between liquid crystalline polyester films by plasma treatment 査読

    Yasuhiro Kurihara, Hiroyuki Ohata, Masahiko Kawaguchi, Shinichi Yamazaki, Kunio Kimura

    Journal of Adhesion Science and Technology   22 ( 16 )   1985 - 2002   2008年10月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    Surface modification of thermotropic liquid crystalline aromatic polyester (LCP) films was carried out by low-pressure plasma treatment to improve the initial adhesion as well as the long-term adhesion reliability, a measure of durability between the LCP films used as substrates for printed circuit boards. Plasma irradiation was carried out in various plasma gases with different plasma modes such as reactive-ion-etching, and direct-plasma (DP) with pressures ranging from 6.7 Pa to 26.6 Pa. The introduction of polar groups on the film surface such as phenolic hydroxyl groups and carboxyl groups enhanced the initial adhesion by increased chemical interaction. However, if the concentration of polar groups became too high, the longterm adhesion reliability estimated by the pressure cooker test was degraded due to the acceleration of the penetration of water molecules into the interface. A large surface roughness was also effective in preventing the decrease in the long-term adhesion reliability. However, too much increase in surface roughness decreases the long-term adhesion reliability. The DP-treatment in the O2 atmosphere at a gas pressure of 6.7 Pa was found to be the best plasma condition for both the initial adhesion as well as the long-term adhesion reliability between the LCP films. © 2008 VSP.

    DOI: 10.1163/156856108X331751

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  • Composition control of aromatic copolyesters by shearing 査読

    Kunio Kimura, Toshimitsu Ichimori, Kanji Wakabayashi, Shin-Ichiro Kohama, Shinichi Yamazaki

    Macromolecules   41 ( 12 )   4193 - 4199   2008年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)  

    Composition control of copolyester was examined by using hydrodynarnically induced phase separation, during solution polymerization, of p-acetoxybenzoic acid and m-acetoxybenzoic acid (m-ABA). Polymerizations were carried out in liquid paraffin at 1.0% of concentration under shear flow. The polymers were obtained as precipitates formed via phase separation of oligomers and the subsequent polymerization in the precipitates. When the feed ratio of m-ABA (χf) was 20 mol %, the molar ratio of m-oxybenzoyl moiety in the precipitated polymers (χp) was 5.3, 3.1, and 2.3 mol % at a shear rate (γ) of 0, 147, and 489 s-1, respectively. The values of χp were much lower than those of χf, and shear flow lowered the value of xp
    thus, controlling shear flow influenced both the reaction rate of the monomers and the miscibility of the oligomers. It especially enhanced the difference on the miscibihty between homo-oligomers and co-oligomers. This change in the miscibility by shear flow brought about the more rapid precipitation of homo-oligomers than co-oligomers, leading to the selective formation of poly(p-oxybenzoyl). © 2008 American Chemical Society.

    DOI: 10.1021/ma800529d

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  • Improvement of adhesion and long-term adhesive reliability of liquid crystalline polyester film by plasma treatment 査読

    Yasuhiro Kurihara, Hiroyuki Ohata, Masahiko Kawaguchi, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF APPLIED POLYMER SCIENCE   108 ( 1 )   85 - 92   2008年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    Surface modification of thermotropic liquid crystalline aromatic polyester (LCP) films was examined by low-pressure plasma treatment to improve initial adhesion and long-term adhesive reliability between the LCP film and an epoxy bonding sheet for printed circuit boards. Plasma irradiation was carried out in various plasma gases with different plasma modes as reactive-ion-etching (RIE), direct-plasma (DP) with pressures ranging from 4.0 to 26.6 Pa. Although the initial adhesion of the DP-treated film increased, the long-term adhesive reliability estimated by pressure cooker test (PCT) decreased with decreasing the plasma gas pressure in every gas. The higher concentration of the generated polar groups such as phenolic hydroxyl group and carboxyl group enhanced the initial adhesion by the increase in the chemical interaction; however, it damaged the long-term adhesive reliability due to the acceleration of the penetration of water molecules into the interface. The large surface roughness was effective to enhance the initial adhesion and the long-term adhesive reliability. The RIE-treatment generated the polar groups and the larger surface roughness than the DP-treatment. The RIE-treatment in the O-2 atmosphere at the gas pressure of 13.3 Pa was the best plasma condition for both the initial adhesion and the long-term adhesive reliability. (C) 2007 Wiley Periodicals, Inc.

    DOI: 10.1002/app.27537

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  • Dimer effect on fractional polycondensation of poly(p-oxybenzoyl) 査読

    Kunio Kimura, Yasuo Shimizu, Toshimitsu Ichimori, Shin-Ichiro Kohama, Shinichi Yamazaki, Yuhiko Yamashita

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   46 ( 5 )   1598 - 1606   2008年3月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    Selective preparation of poly(p-oxybenzoyl) (POB) crystals was examined from the viewpoint of a dimer effect on fractional polycondensation. Four different copolymerization systems were chosen as the combinations of p-acetoxybenzoic acid (p-ABA), m-acetoxybenzoic acid (m-ABA), and their dimers. The crystals obtained from the copolymerization of the dimer of p-ABA (p-ABAD) and m-ABA contained only 3.1 mol % of m-oxybenzoyl moiety even at high content of m-oxybenzoyl moiety in feed (chi(f)) of 40 mol %. p-Oxybenzoyl homo-oligomers were more rapidly formed from p-ABAD in the solution than from p-ABA, and they were crystallized to form the crystals with segregating co-oligomers. While co-oligomers containing more m-oxybenzoyl moiety were formed in the solution, afterward they were unable to be phase-separated because of higher miscibility. The further polycondensation proceeded in the precipitated crystal, and finally the POB crystal was selectively formed. Lower polymerization temperature and concentration enhanced the fractionability, and the POB crystals containing less than 1 mol % m-oxybenzoyl moiety were prepared at chi(f) of 30 mol %, 270 degrees C, and a concentration of 0.5%. The dimer effect on the fractional polycondensation was clearly observed. (C) 2008 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.22496

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  • Nonstoichiometric Synthesis of Poly(4,4’-oxydiphenylene pyromelliteimide) by Reaction-Induced Crystallization of Oligomers 査読

    Kanji Wakabayashi, Shin-ichiro Kohama, Shinichi Yamazaki, Kunio Kimura

    Macromolecules   41 ( 4 )   1168 - 1174   2008年

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    記述言語:英語  

    DOI: 10.1021/ma702030u

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  • Preparation of Poly(4'-oxy-4-biphenylcarbonyl) Needle-like Crystals with the Aid of Copolymerization 査読

    Naomi Yoshida, Yasuhiro Kurihara, Shin-ichiro Kohama, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    Macromolecules   41 ( 20 )   7571 - 7578   2008年

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    DOI: 10.1021/ma800029n

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  • Fluorinated Poly(aryl thioether)s and Poly(aryl sulfone)s Derived from 2,3,4,5,6-Pentafluorobenzoic Acid 査読

    Shunsuke Masaki, Natsuko Sato, Ai Nishichi, Shinichi Yamazaki, Kunio Kimura

    J. Appl. Polym. Sci.   108 ( 1 )   498 - 503   2008年

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    記述言語:英語  

    DOI: 10.1002/app.27347

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  • Morphology control of poly(2,2’-phenylene-5,5’-bibenzimidazole) by reaction-induced crystallization during polymerization 査読

    Shin-ichiro Kohama, Jin Gong, Kazuya Kimura, Shinichi Yamazaki, Tetsuya Uchida, Kaoru Shimamura, Kunio Kimura

    Polymer   49 ( 7 )   1783 - 1791   2008年

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    記述言語:英語  

    DOI: 10.1016/j.polymer.2008.02.016

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  • Preparation of Poly(4-phthalimide) Nanoribbon by Reaction-Induced Crystallization 査読

    Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    Macromolecules   41 ( 13 )   4607 - 4614   2008年

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    記述言語:英語  

    DOI: 10.1021/ma800874w

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  • Preparation of Brush-like Crystals of Poly[2,6-(1,4-phenylene)-benzobisimidazole] 査読

    Jin Gong, Shin-ichiro Kohama, Kazuya Kimura, Shinichi Yamazaki, Kunio Kimura

    Polymer   49 ( 18 )   3928 - 3937   2008年

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    記述言語:英語  

    DOI: 10.1016/j.polymer.2008.07.011

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  • Morphological architecture of poly(p-oxybenzoyl) by modification of oligomer end-group 査読

    Kunio Kimura, Yasuhiro Kurihara, Hideki Omori, Shin-ichiro Kohama, Shinichi Yamazaki, Yuhiko Yamashita

    POLYMER   48 ( 12 )   3429 - 3436   2007年6月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ELSEVIER SCI LTD  

    Influence of oligomer end-group on morphology of poly(4-oxybenzoyl) (POB) was examined by polymerizations of 4-acyloxybenzoic acids having different acyl groups. Polymerizations of 4-propionyloxybenzoic acid, 4-hexanoyloxybenzoic acid, 4-octanoyloxybenzoic acid and 4-decanoyloxybenzoic acid in liquid paraffin at 320 degrees C yielded needle-like or pillar-like POB crystals via crystallization of oligomers. On the other hand, the polymerization of 4-perfluorooctanoyloxybenzoic acid (FOBA) afforded microspheres having needle-like crystals on the surfaces. At an initial stage in the polymerization, microspheres having smooth surface were formed via liquid-liquid phase separation of oligomers prepared from FOBA owing to the low miscibility of perfluorooctanoyl end-group. Thereby the phase-separation behaviour of oligomers changed from liquid-liquid phase separation to crystallization at a middle stage in the polymerization and then needle-like crystals were formed on the surface of the microspheres. Chemical structure of the oligomer end-group affected significantly the phase-separation behaviour of oligomers and ultimately the morphology of POB. (C) 2007 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2007.04.025

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  • Morphology control of various aromatic polyimides by using phase separation during polymerization 査読

    Kanji Wakabayashi, Shin-ichiro Kohama, Shinichi Yamazaki, Kunio Kimura

    Polymer   48 ( 2 )   458 - 466   2007年

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    記述言語:英語  

    DOI: 10.1016/j.polymer.2006.11.061

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  • Synthesis and properties of fluorine-containing poly(aryl ether oxadiazole)s 査読

    Natsuko Sato, Ken Tanaka, Shunsuke Masaki, Shinichi Yamazaki, Kunio Kimura, Ai Nishichi

    J. Polym. Sci., Part A: Polym. Chem.   45 ( 14 )   2855 - 2866   2007年

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    記述言語:英語  

    DOI: 10.1002/pola.22041

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  • Fabrication of Particles and Crystals of Poly(p-phenylene pyromelliteimide) and Study on Crystal Structure 査読

    Kunio Kimura, Shin-ichiro Kohama, Kanji Wakabayashi, Shinichi Yamazaki, Tetsuya Uchida

    Macromolecules   40 ( 2 )   239 - 246   2007年

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    記述言語:英語  

    DOI: 10.1021/ma062032y

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  • Selective preparation of poly(p-oxybenzoyl) by using fractional polycondensation 査読

    K Kimura, SI Kohama, J Kuroda, Y Shimizu, T Ichimori, Y Yamashita

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   44 ( 8 )   2732 - 2743   2006年4月

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    Selective preparation of poly(p-oxybenzoyl) (POB) in the copolymerization system of p-acetoxybenzoic acid (p-ABA) and m-acetoxybenzoic acid (m-ABA) was examined by using reaction-induced crystallization of oligomers. Polymer crystals mainly composed of p-oxybenzoyl moiety were precipitated when. the content of m-ABA in the feed was 30 mol %. The formation of the polymer crystals was attributed to both the reactivity of monomer and the phase-separation behavior of oligomer. Reactivity of p-ABA was twice higher than that of m-ABA, and thereby, the homo-oligomers of p-oxybenzoyl moiety were more rapidly formed in solution than do co-oligomers at the early stage in polymerization. They were selectively precipitated by crystallization to form crystals because of low miscibility. Co-oligomers containing m-oxybenzoyl moiety were also formed in solution, but they were unable to be phase-separated because of higher miscibility. Further polycondensation occurred between oligomers in the precipitated crystals, leading to the formation of POB. This polymerization proceeded with selecting certain monomers by crystallization and afforded a new methodology for fractional polycondensation. (c) 2006 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.21375

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  • Fabrication of poly(p-oxycinnamoyl) nano-scale particles 査読

    Yoshito Hirai, Shin-Ichiro Kohama, Shinichi Yamazaki, Kunio Kimura

    Journal of Fiber Science and Technology   62 ( 7 )   167 - 174   2006年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Society of Fiber Science and Technology  

    Fabrication of poly(p-oxycinnamoyl) (POC) nano-scale particles was examined by using self-seeding polymerization of (E)-4-acetoxycinnamic acid in liquid paraffin. The diameter of the POC spheres was very susceptible to the polymerization temperature and the temperature drop was very efficient to control the nucleation process by the adjustment of the degree of super saturation leading to the decrease in the diameter. The average diameter of the spheres prepared at 320°C was 3.6 μm, whereas, the temperature drop from 320°C to 250°C just before the nucleation afforded the POC microspheres having average diameter of 2.2 μm. In order to prepare the nano-scale particles, only the self-seeding polymerization was not sufficient and the control of the growth process was additionally required. The POC particles having 600 nm of the average diameter were obtained by not only the temperature change from 320°C to 250°C and then 320°C but also the addition of 4-octadecyloxybiphenyl as a coalescence inhibitor. The average diameter was in nano-scale, but the diameter distribution became broader with bimodality.

    DOI: 10.2115/fiber.62.167

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  • Novel fluorine-containing poly(aryl ether amide)s derived from 2,3,4,5,6-pentafluorobenzoic acid 査読

    Ken Tanaka, Natsuko Sato, Shinichi Yamazaki, Kunio Kimura, Yuhiko Yamashita

    Sen’i Gakkaishi   62 ( 7 )   155 - 161   2006年

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    記述言語:英語  

    DOI: 10.2115/fiber.62.155

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  • Consideration of solvent effect on precipitation polymerization of poly(ether-ketone)s via Friedel-Craft acylation 査読

    Manabu Ohmori, Kunio Kimura, Yuhiko Yamashita, Yoshimitsu Sakaguchi

    Journal of Fiber Science and Technology   62 ( 7 )   141 - 149   2006年

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    記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:Society of Fiber Science and Technology  

    Precipitation polymerization of diphenyl ether and isophthaloyl chloride catalyzed by AlCl3 via Friedel-Crafts acylation was examined in various solvents to clarify the polymerization behavior. Polymerizations were carried out in three categorized solvents based on the solubility to both catalyst and polymer, which were cyclohexane (CH), 1,2-dichloroethane (DCE) and DCE containing 2 wt% nitrobenzene (2%-NB). In DCE which was widely used, the oligomers were precipitated as a form of the complex with AlCl3 at the early stage of polymerization. The precipitates of the oligomers were swollen by the solvent, in which any short-range regular structure did not exist. The further polymerization proceeded even in the precipitates with eliminating by-produced HCl, and high molecular weight poly(ether-ketone)s (PEK) were finally formed. Nevertheless the reaction in 2%-NB yielded the well-swollen precipitates, the high molecular weight PEK was not synthesized in the precipitates because the reaction was terminated by not only the inefficient elimination of HCl due to the higher solubility of HCl but also the deactivation of catalyst by coordination of NB to AlCl3. Although the precipitation occurred more readily in CH due to the lower solubility of oligomers, the polymer was not synthesized in the precipitates. The resulting precipitates comprised of the dimers were not swollen in this case, and thereby it was very difficult to react between dimers and eliminate HCI from the precipitates. The solvents having high miscibility to catalyst and the polymers, low solubility of HCl gas, and no basicity are necessary for making high molecular weight polymers via the precipitation polymerization.

    DOI: 10.2115/fiber.62.141

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  • Preparation and mechanical properties of rigid polymer network/nylon6 composites 査読

    T Uchida, K Shimantura, K Kimura

    SEN-I GAKKAISHI   59 ( 6 )   207 - 212   2003年6月

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    記述言語:日本語   掲載種別:研究論文(学術雑誌)   出版者・発行元:SOC FIBER SCIENCE TECHNOLOGY  

    Rigid polymer networks were prepared by polycondensation of 2,5-diamino-1,4-benzenedithiol with a mixture of tereplithalic acid (TPA) and trimesic acid (TMA). The apparent density was dependent on TPA/TMA ratio and much less than that of linear PBZT (1.57 g/cm(3)), showing existence of many nano voids within the network. As the segment was so rigid, many COOH's were left around the voids. The network swelled twice in weight with E caprolactam, which was polymerized into a composite form of nylon6 impregnated rigid polymer network. Extraction of free nylon6 from the composite with formic acid showed that a quarter of nylon6 grafted directly to rigid polymer network. The grafted nylon6 could not crystallize evidenced by DSC measurements. On the other hand, particles of PBZT network (several hundred nm in diameter) were prepared by stopping the polycondensation just before gelation. A composite film was prepared with the particles swollen with epsilon-caprolactam. The ratio of PBZT network/nylon6 was 1/3 and the apparent density of the composite film was 1.23 g/cm(3) which is higher than that of a pure nylon6 film (1.16 g/cm(3)). Significant improvement in the mechanical property was observed for this composite.

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▼全件表示

書籍等出版物

  • Polymer Whisker

    1994年 

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  • 高分子ウィスカー

    フィラー活用辞典  1994年 

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MISC

  • アラミドの中空微粒子の新調製法 招待

    木村邦生, 山崎慎一, 内田哲也, 中山博文

    ケミカルエンジニヤリング   59 ( 12 )   1   2014年

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    記述言語:日本語   掲載種別:記事・総説・解説・論説等(商業誌、新聞、ウェブメディア)  

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  • Preparation of High-Performance Polymer Spheres by Using Phase-Separation During Solution Polymerization

    Kunio Kimura, Shinichi Yamazaki, Tetsuya Uchida

    Proc. Society for the Advancement of Material and Process Engineering Symposium   44   11   2012年

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  • Fabrication of Rod-like Crystals of Poly(p-oxycinnamoyl) by Hydrodynamically Induced Crystallization during Solution Polymerization 査読

    Shin-ichiro Kohama, Mayuko Muraoka, Shinichi Yamazaki, Kunio Kimura

    Sen’i Gakkaishi   64 ( 8 )   216 - 219   2008年

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    記述言語:英語   掲載種別:記事・総説・解説・論説等(学術雑誌)  

    DOI: 10.2115/fiber.64.220

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  • Fabrication of nanoribbon of high-performance polyamide

    K.Wakabayashi, S.Yamazaki, T.Uchida, K.Kimura

    Polymer Preprints, Div. of Polymer Chem.   235   507   2008年

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  • Morphology control of aromatic polymers in concert with polymerization 査読

    Kunio Kimura, Shin-ichiro Kohama, Shinichi Yamazaki

    POLYMER JOURNAL   38 ( 10 )   1005 - 1022   2006年

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    記述言語:英語   掲載種別:書評論文,書評,文献紹介等   出版者・発行元:NATURE PUBLISHING GROUP  

    Morphology control methods of aromatic polymers in concert with polymerization reaction are described in this review. Many attractive methods have been developed including reaction-induced phase separation of oligomers, epitaxial polymerization, shear-induced chain orientation during gelation, template-based polymerization, suspension polycondensation, solid-state polycondensation and liquid-liquid interfacial precipitation and so on. Among them, the reaction-induced phase separation of oligomers, in which there are two modes of crystallization and liquid-liquid phase separation, possess practically high potentiality to create novel polymer materials since it can control not only the morphology but also the molecular chain orientation. Ultimate goal is the embodiment of the nature system in a flask, that is, the control of the materials from primary structures to super structures. The morphology control methods by using polymerization reaction afford the valuable methodology for the three-dimensional structure architecture.

    DOI: 10.1295/polymj.PJ2006083

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  • Fabrication of poly(2-oxy-6-naphthoyl) particles by direct polycondensation of 2-hydroxy-6-naphthoic acid

    K Kimura, T Horii, S Kohama, Y Yamashita

    POLYMERS FOR ADVANCED TECHNOLOGIES   16 ( 9 )   693 - 697   2005年9月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS LTD  

    Morphology control of poly(2-oxy-6-naphthoyl) (PON) was examined by using reaction-induced crystallization of oligomers during direct polycondensation of 2-hydroxy-6-naphthoic acid with p-toluenesulfonyl chloride and NN-dimethylformamide in pyridine. PON particles were obtained of which the diameter was in the range of 8.0-8.3 mu m. The particles were comprised of many lamellae and exhibited spherulitic morphology. They possessed high crystallinity evaluated from wide-angle X-ray scattering (WAXS). Formation mechanism of the particles was clarified from the results of morphology observation, yield, density and WAXS. When the number average degree of polymerization of the oligomers exceeded a critical value of ca. 4-5, they were precipitated to form lamellae. The lamellae grew to spherulites through screw dislocation with continuous precipitation of the oligomer from the solution. Finally, further polymerization occurred gradually in the precipitates. Copyright (c) 2005 John Wiley & Sons, Ltd.

    DOI: 10.1002/pat.635

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  • Novel optical CO2 sensing material: pH indicator immobilized in fluorine-containing poly(aryl ether ketone) films

    Y Amao, T Komori, Y Tabuchi, Y Yamashita, K Kimura

    SENSOR LETTERS   3 ( 2 )   168 - 173   2005年6月

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    記述言語:英語   出版者・発行元:AMER SCIENTIFIC PUBLISHERS  

    A series of new fluorine-containing poly(aryl ether ketone)s (8F-PEKEK(Ar); Ar: 2-2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane (6FBA), 2,2-bis(4-hydroxyphenyl)propane (BA), 2-(4-hydroxyphenyl)-2-(3-hydroxyphenyl)propane (3,4'-BA) or 9,9'-bis(4-hydroxyphenyl)fluorine (HF)) are synthesized and applied to the matrix of optical CO2 sensor based on the overlay of the CO2 induced absorbance change of pH indicator dye alpha-naphtholphthalein with the fluorescence of tetraphenylporphyrin (TPP) was developed. The observed luminescence intensity from TPP at 655 nm increased with increasing the CO2 concentration. The ratio I-100/I-0 values of the sensing films consisting of a-naphtholphthalein in 8F-PEKEKs layer and TPP in polystyrene layer, where I-0 and I-100 represent the detected luminescence intensities from a layer exposed to 100% argon and 100% CO2, respectively, that the sensitivity of the sensor, are more than 3.6. The response and recovery times of the sensing films consisting of a-naphtholphthalein in 8F-PEKEKs layer and TPP in polystyrene layer were less than 8.6 s for switching from argon to CO2, and for switching from CO2 to argon. The signal changes were fully reversible and no hysterisis was observed during the measurements. The highly sensitive and fast responsible optical CO2 sensor based on fluorescence intensity changes of TPP due to the absorption change of a-naphtholphthalein in 8F-PEKEKs layer with CO2 was achieved.

    DOI: 10.1166/sl.2005.014

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  • Nonstoichiometric polycondensation of 4-acetoxybenzoic acid in the presence of monoacetate

    SI Kohama, K Kimura, Y Yamashita

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   43 ( 9 )   1757 - 1766   2005年5月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS INC  

    Nonstoichiometric polycondensation of 4-acetoxybenzoic acid (ABA) was examined in the presence of three kinds of aromatic monoacetates: 4-hexyloxyphenyl acetate, 4-decyloxyphenyl acetate, and 4-octadecyloxyphenyl acetate. Polymerizations were carried out in liquid paraffin at 320 degrees C under nonstoichiometric conditions, in which the acetoxy group was in large excess of the carboxyl group. Poly(4-oxybenzoyl) (POB) was obtained as crystal at the molar ratio of monoacetates in feed (chi) of less than 80 mol%, meaning that the concentration of the acetoxy group was five times that of the carboxylic group. The obtained POB possessed much higher number average degree of polymerization (DPn), ranging from 353 to 467, than the calculated DPn on the basis of X. High molecular weight polymer was synthesized even under nonstoichiometric conditions via crystallization of oligomers and the following solid-state polymerization in the crystals. (c) 2005 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.20651

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  • Novel network morphology of poly(p-oxybenzoyl)

    K Kimura, S Kohama, S Kondoh, T Uchida, Y Yamashita, T Oohazama, Y Sakaguchi

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   43 ( 8 )   1624 - 1634   2005年4月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS INC  

    Polymerization of 4-acetoxybenzoic acid (ABA) with 3,5-diacetoxybenzoic acid (DABA) was examined to control the morphology of poly(p-oxybenzoyl) (POB). Polymerizations were carried out at a concentration of 1.0% in an aromatic solvent Therm S-1000 (R) (mixture of dibenzyltoluene) at 320 degrees C. Polymerization of ABA yielded the POB fibrillar crystals, but the polymerization with DABA at a concentration in the feed (chi(f)) of 0.10-0.15 afforded novel network structures comprised of spheres connected by fibrillar crystals. The diameter of the spheres prepared at chi(f) of 0. 15, which were 0. 7 and 5.0 mu m, showed bimodality. The network distance, fibril length, and fibril width were 6.1, 2.6, and 0.1 mu m, respectively. They possessed high crystallinity. The network structure was formed as follows. Co-oligomers were first precipitated in the beginning of the polymerization by liquid-liquid phase separation to form the microdroplets. The fibrillar crystals were formed in the coalesced spheres by the crystallization of oligomers induced by the increase of molecular weight. The fibrillar crystals connecting the spheres gradually appeared owing to the shrinkage of the spheres. The fibrillar crystals grew from the surface of the spheres with the crystallization of homo-oligomers of 4-oxybenzoyl units, and finally the network structure was completed. (c) 2005 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.20639

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  • Preparation of well-oriented poly(p-phenylene pyromelliteimide) fiber via shear-induced orientation of poly(amic ethyl ester) precursor during polymerization

    JH Zhuang, K Kimura, CE Xia, Y Yamashita

    HIGH PERFORMANCE POLYMERS   17 ( 1 )   35 - 50   2005年3月

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    記述言語:英語   出版者・発行元:SAGE PUBLICATIONS LTD  

    The orientation of poly(p-phenylene pyromelliteimide) (PPPI) molecules was examined by means of shearing during the gelation of poly(amic ethyl ester) (PAEE) precursor and thermal imidization. The polymerization of 1,4-phenylene diamine (PPDA) and 2,5-diethoxycarbonyl-1,4-benzenedicarbonyl chloride (DEBC), and that of N,N'-bis(trimethylsilyl)-1,4-phenylenediamine (N-silyl-PPDA) and DEBC yielded the PAEE gel during polymerization. With respect to the polymerization of PPDA and DEBC, 0.44 mol L-1 gave the highest DPn of PAEE. at the gelation point, and the strong shear during gelation made the PAEE and ultimately PPPI molecular chains oriented in the planar mode. In contrast to this, the polymerization of N-silyl-PPDA and DEBC gave a higher DPn of PAEE at the gelation point than that of PPDA and DEBC. The strong shear stress applied to the PAEE gel, prepared at 0.50 mol L-1, induced the uni-axial orientation of the molecular chains, but the relaxation of the orientation occurred gradually with time. The addition of ethyl acetate to the gel prevented the relaxation of the chain orientation and accelerated the crystallization. As a result, uni-axial orientation of the PAEE molecular chains was induced along the shear direction in the gel rather than the planar mode, and ultimately the PPPI molecular chains were well-oriented.

    DOI: 10.1177/0954008305044618

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  • Polymer whiskers based on p-mercaptobenzoyl and p-oxybenzoyl blocks

    K Kobashi, K Kimura, T Uchida, Y Yamashita, K Shimamura

    POLYMER   46 ( 7 )   2191 - 2200   2005年3月

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    記述言語:英語   出版者・発行元:ELSEVIER SCI LTD  

    Preparation of polymer whisker based on p-mercaptobenzoyl (S) and p-oxybenzoyl (0) blocks was examined by the polymerization of Sacetyl-4-mercaptobenzoic acid (AMBA) and the following addition of 4-acetoxybenzoic acid (ABA). Polymerization of AMBA was carried out in liquid paraffin at 300 degrees C for 3 h yielding poly(p-mercaptobenzoyl) (PMB) whisker, and then ABA was added stepwise at 3-hour intervals into the solution. Initial polymerization concentration was 1.98%. The length of the whisker increased with the addition and it became 26.7 mu m from 20.1 mu m after third ABA addition. The width increased very slightly. Both length and width increased with polymer yield but the length increased preferentially rather than the width. The number of whiskers was constant even after the addition of ABA and poly (p-oxybenzoyl) (POB) whisker was not newly formed by the addition. Microscopic FT-IR and selected area electron diffraction measurements revealed that polymer molecules were aligned along the long axis of the whiskers, and the center and tip parts were comprised of PMB crystal and POB crystal, respectively. The polymer whisker based on S and 0 blocks was successfully prepared as grafting POB crystal on PMB whisker with stepwise addition of ABA. Thermal property of the resulting whiskers was also discussed. (c) 2005 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2005.01.016

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  • Morphology control of poly(p-mercaptobenzoyl) by modification of oligomer end-group.

    K Kimura, D Nakajima, K Kobashi, S Kohama, Y Yamashita, T Uchida

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   229   U949 - U949   2005年3月

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    記述言語:英語   掲載種別:研究発表ペーパー・要旨(国際会議)   出版者・発行元:AMER CHEMICAL SOC  

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  • Morphology of poly(p-oxycinnamoyl) formed by hydrodynamically induced crystallization during solution polymerization.

    K Kimura, M Muraoka, Y Yamashita, T Uchida

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   229   U949 - U950   2005年3月

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    記述言語:英語   掲載種別:研究発表ペーパー・要旨(国際会議)   出版者・発行元:AMER CHEMICAL SOC  

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  • Direct synthesis of poly(4’-oxy-4-biphenylcarboxyl) and poly(2-oxy-6-naphthoyl) under nonstoichiometric condition

    Polymer International   54 ( 2 )   471 - 480   2005年2月

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  • Morphology of poly(p-oxybenzoyl) prepared in perfluoropolyether

    K Kimura, H Ohmori, T Uchida, Y Yamashita

    POLYMERS FOR ADVANCED TECHNOLOGIES   16 ( 1 )   6 - 10   2005年1月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS LTD  

    Solvent effect on the morphology of poly(p-oxybenzoyl) (POB) prepared by the reaction-induced phase separation of oligomers was examined by the polymerization of p-acetoxybenzoic acid in perfluoropolyether Aflunox(TM) (AFL2507 and AFL606). Polymerization was carried out at 320degreesC for 6 hr. POB microspheres were formed in AFL2507 by the liquid-liquid phase separation of oligomers due to the low miscibility of oligomers in AFL2507. The molecular weight of the solvent influenced the morphology, and the polymerization in AFL606 of which the molecular weight was lower than AFL2507 yielded whiskers formed by crystallization of oligomers induced by the increase in miscibility compared with that in AFL2507. The solvent structure and its molecular weight influenced the miscibility of oligomers and ultimately controlled the morphology from whisker to microsphere. Copyright (C) 2004 John Wiley Sons, Ltd.

    DOI: 10.1002/pat.540

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  • New attempt at the stereoselective polymerization of lactide by using crystallization during polymerization

    A Ando, K Kimura, Y Onda, Y Yamashita

    MACROMOLECULAR RAPID COMMUNICATIONS   26 ( 2 )   98 - 102   2005年1月

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    記述言語:英語   出版者・発行元:WILEY-V C H VERLAG GMBH  

    The stereoselective polymerization of partial rac-lactide was attempted by using crystallization during polymerization. Polymerizations were carried out with trifluoromethanesulfonic acid in a mixed solvent of toluene and octane. The molar content Of L-lactate in the feed was 95%. Polymerization proceeded with the elimination of D-lactate by means of crystallization. Poly(L-lactic acid) (PLLA) crystals were first precipitated and then plate-like poly(lactic acid) (PLA) crystals were finally obtained, of which the composition Of L-lactate was 97.6% and the (M) over bar (n) was 1.68 x 10(4).

    DOI: 10.1002/marc.200400428

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  • Morphology control of poly(p-mercaptobenzoyl) by modification of oligomer end-group

    K Kimura, D Nakajima, K Kobashi, S Kohama, T Uchida, Y Yamashita

    POLYMER JOURNAL   37 ( 7 )   471 - 479   2005年

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    記述言語:英語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    Influence of acyl end-group of oligomers on morphology of poly (p-mercaptobenzoyl) (PMB) was examined by the polymerization of S-acyl-4-mercaptobenzoic acids having the different acyl groups and their dimers in liquid paraffin at 260-300 degrees C. The polymerization of S-acetyl-4-mercaptobenzoic acid afforded PMB whiskers, whereas the polymerization of S-propionyl-4-mercaptobenzoic acid, S-butyryl-4-mercaptobenzoic acid and S-valeryl-4-mercaptobenzoic acid yielded PMB microspheres. The microspheres were formed by the liquid-liquid phase separation of oligomers induced by the longer acyl end-groups than acetyl group of the oligomers due to the reduction of freezing point of oligomers. In contrast to this, the polymerizations of their dimers afforded needle-like and slab-like crystals instead of microspheres. In these polymerizations, the crystallization was induced due to the increase of the molecular weight of the phase-separated oligomers, leading to the increase of the freezing point of oligomers. The morphology of PMB could be controlled by the chemical modification of oligomer end-groups.

    DOI: 10.1295/polymj.37.471

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  • Fabrication of poly(p-oxybenzoyl) nanowhisker

    K Kimura, S Yamazaki, Y Matsuoka, Y Yamashita

    POLYMER JOURNAL   37 ( 12 )   906 - 912   2005年

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    記述言語:英語   出版者・発行元:NATURE PUBLISHING GROUP  

    Fabrication of poly(p-oxybenzoyl) (POB) nanowhiskers was examined by using reaction-induced crystallization of oligomers during the polymerization of p-acetoxybenzoic acid in liquid paraffin. Width of the POB whiskers was susceptible to polymerization temperature and it was efficiently controlled by a change in temperature during the polymerization. Increase in polymerization temperature just after nucleation (Han) reduced the degree of super saturation of oligomers (or) resulting in the depression of the width increase by the crystallization of oligomers on side surface of the whiskers. Temperature drop just before nucleation (Cbn) enhanced the value of a resulting in the generation of much more nuclei having the smaller width. On the basis of these results, the combination of these two methods Han and Cbn afforded the whiskers having the smallest width, and the POB nanowhiskers were prepared of which the width and the length were 190nm and 18.6 mu m, respectively.

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  • Morohology Control of Poly(p-mercaptobenzoil)by Modification of Ologomer End-group

    K.Kimura, D.Nakajima, K.Kobashi, S.Kohama, T.Uchida, Y.Yamashita

    Polymer Preprints   46 ( 1 )   694 - 695   2005年

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  • Polymer whiskers composed of p-oxybenzoyl and p-mercaptobenzoyl having graded compositions

    K Kobashi, K Kimura, Y Yamashita

    MACROMOLECULES   37 ( 20 )   7570 - 7577   2004年10月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    Preparation of polymer whiskers composed of p-oxybenzoyl (O) units and p-mercaptobenzoyl (S) units having graded composition was examined by the polymerization of S-acetyl-4-mercaptobenzoic acid (AMBA) and 4-(4-acetoxybenzoyloxy)benzoic acid (OO) or 4-[4-(4-acetoxybenzoyloxy)benzoyloxy]benzoic acid (OOO). Polymerizations were carried out in liquid paraffin at 300 degreesC for 6 h. The polymerization concentration was 1.0% and the molar ratio of O units in feed was 50%. Polymerization of AMBA and OO yielded copolymer whiskers by means of the crystallization of oligomers, which were 15 mum in average length and 0.4 mum in average width. The length and the width increased with polymer yield but the length increased preferentially rather than the width. The number of whiskers was constant during polymerization. The content of O units in the whiskers (chi(O)) prepared for 8 min was 62 mol % and then decreased to 49 mol % after 6 h. This fact revealed that the center part of the whisker was rich in O units, and the outer and tip parts were rich in S units. This whisker possessed a graded composition from O units to S units along the directions of the length and width. The oligomers rich in O unit sequences were preferentially precipitated in the early stage of polymerization, and afterward the oligomers poor in O units were precipitated to form the whiskers leading to a graded composition. Polymerization of AMBA and OOO yielded copolymer whiskers with a larger gradient composition than that of whiskers prepared from AMBA and OO.

    DOI: 10.1021/ma035962f

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  • Influence of short distance sequence regularity on preparation of poly(p-oxybenzoyl-co-p-mercaptobenzoyl) whisker

    K Kobashi, K Kimura, Y Yamashita

    POLYMER   45 ( 21 )   7099 - 7107   2004年9月

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    記述言語:英語   出版者・発行元:ELSEVIER SCI LTD  

    Preparation of the poly (p-oxybenzoyl -co-p-mercaptobenzoyl) whiskers was examined by means of the crystallization of oligomers during solution polymerization. Polymerizations were carried out in liquid paraffin at the concentration of 1.0% and 300 degreesC for 6 h. Copolymerization of 4-acetoxybenzoic acid and S-acetyl-4-mercaptobenzoic acid did not yield the whiskers. This was attributed to tendency that the copolymerization reduced the crystallizability of oligomers and induced the liquid-liquid phase separation of oligomers due to the lower freezing point. In order to induce short distance sequence regularity into oligomers, copolymerizations of two among four monomers were conducted, which were 4-(4-acetoxybenzoyl)oxybenzoic acid, S-(4-acetoxybenzoyl)-4-mercaptobenzoic acid, 4-(S-acetyl-4mercaptobenzoyl)oxybenzoic acid and S-(S-acetyl-4-mercaptobenzoyl)-4-mercaptobenzoic acid. The copolymerizations of two of these monomers yielded the whiskers but for that of 4-(4-acetoxybenzoyl)oxybenzoic acid and S-(S-acetyl-4-mercaptobenzoyl)-4-mercaptobenzoic acid. The short distance sequence regularity of oligomers brought about the crystallization of oligomers, leading to the formation of whiskers. (C) 2004 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2004.08.017

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  • Synthesis of thermally crosslinkable fluorine-containing poly(arylene ether ketone)s - II. Propargyl ether terminated poly(arylene ether ketone)s

    K Kimura, A Nishichi, Y Yamashita

    POLYMERS FOR ADVANCED TECHNOLOGIES   15 ( 6 )   313 - 319   2004年6月

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    記述言語:英語   出版者・発行元:WILEY-BLACKWELL  

    Novel thermally crosslinkable fluorine-containing poly(arylene ether ketone)s comprised of 2,3,5, 6-tetrafluoro-1,4-phenylene moiety were synthesized by the termination of polymer chain ends with propargyl ether groups in order to improve solvent resistance. Crosslinking reaction occurred over 250 C through the formation of both chromen ring and polyene structure. This structure change brought about not only the outstanding solvent resistance but also the increase in glass transition temperature (T-g). The cured films also exhibited excellent thermal stability, transparency and hydrophobicity derived from fluorine atoms. Copyright (C) 2004 John Wiley Sons, Ltd.

    DOI: 10.1002/pat.476

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  • Preparation of poly(p-oxybenzoyl) microspheres having needlelike crystals on the surface

    K Kimura, S Kohama, S Kondoh, Y Yamashita, T Uchida, T Oohazama, Y Sakaguchi

    MACROMOLECULES   37 ( 4 )   1463 - 1469   2004年2月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    Polymerization of 4-acetoxybenzoic acid (ABA) with 3,5-diacetoxybenzoic acid (DABA) was examined to create a novel morphology of poly(p-oxybenzoyl) (POB) by means of the phase separation of oligomers during polymerization. Polymerizations were carried out at a concentration of 1.0% in liquid paraffin at 320 degreesC. Polymerization of ABA yielded the POB whiskers. On the other hand, the polymerization of ABA with DABA of which the concentration in the feed (chi(f)) was 0.05-0.20 yielded the microspheres having needlelike crystals on the surface. The average diameter of the microspheres was in the range of 3.4-1.6 mum and the average length of the needlelike crystals was 3.2-0.3 mum. The diameter and length decreased with chi(f). DABA acted as a liquid-liquid phase separation inducer and the liquid-liquid phase separation of co-oligomers comprising 4-oxybenzoyl units and 3,5-dioxybenzoyl units was induced in the beginning of polymerization to form the core microspheres. Then the phase separation mode was changed to the crystallization of the homooligomers of the 4-oxybenzoyl unit and the homooligomers were crystallized as needlelike crystals on the surface of microspheres already precipitated. Solid-state polymerization occurred in the precipitates. The microspheres having needlelike crystals were prepared by the combination of liquid-liquid phase separation and the crystallization of oligomers during solution polymerization. The obtained microspheres having needlelike crystals possessed very high crystallinity and exhibited good thermal stability.

    DOI: 10.1021/ma035672z

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  • Influence of electron beam irradiation on properties of fluorine-containing poly(aryl ether ketone)s

    K Kimura, Y Tabuchi, A Nishichi, Y Yamashita, Y Okumura, K Omote, Y Morita, H Kudo

    JOURNAL OF APPLIED POLYMER SCIENCE   91 ( 1 )   157 - 166   2004年1月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS INC  

    The influence of electron beam irradiation on the properties of fluorine-containing poly(aryl ether ketone)s (F-PEK), derived from 2,3,4,5,6-pentafluorobenzoic acid, was examined. Irradiation was performed with an electron beam at a dose of 3.63 x 10(3) Gy s(-1) for which the corresponding doses were 29.0, 51.0, and 94.5 MGy. Tensile strength at break increased up to a dose of 29.0 MGy and then decreased very slightly with irradiation. Elongation at break was more susceptible to irradiation and decreased drastically to one tenth at a dose of 29.0 MGy. Young's modulus was enhanced by the irradiation. F-PEKs were changed from elastic materials to strong and brittle materials by irradiation. Relaxation of the viscoelastic property shifted toward higher temperature by irradiation. These tensile and viscoelastic property changes were attributed to the formation of a bulkier and more rigid structure by crosslinking. The fluorine atoms attached to the 1,4-phenylene moiety in F-PEKs were surprisingly susceptible to the irradiation and were completely lost at a dose of 29.0 MGy. The 7T-electron conjugated aromatic structure was concurrently developed during irradiation. Further, polar functional groups such as carboxyl group and ester group were generated by chain scission and rearrangement. The F-PEKs retained their good transparency and the thermal stability was significantly improved after irradiation. (C) 2003 Wiley Periodicals, Inc.

    DOI: 10.1002/app.13119

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  • Diameter control of poly(p-oxycinnamoyl) microspheres prepared by self-organizing polycondensation

    K Kimura, S Kohama, Y Yamashita, T Uchida, Y Sakaguchi

    POLYMER   44 ( 24 )   7383 - 7387   2003年11月

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    記述言語:英語   出版者・発行元:ELSEVIER SCI LTD  

    The diameter control of poly(p-oxycinnamoyl) (POC) microspheres was examined. POC microspheres were prepared by the polycondensation of (E)-4-acetoxycinnamic acid in liquid paraffin at 320 degreesC. The microspheres were formed through the formation of microdroplets by the reaction-induced liquid-liquid phase separation and the subsequent polymerization of oligomers in the microdroplets leading to the solidification. The size of the microspheres was actually governed by the coalescence of the microdroplets in the growth process. In order to control the coalescence of the microdroplets, 4-octadecyloxybiphenyl (ODB) was added to the polymerization solution as a coalescence inhibitor, which exhibited amphiphilicity to liquid paraffin and POC. ODB inhibited the coalescence of the microdroplets. The average diameter decreased with the increase of the ODB concentration, and it was tunable from 0.97 to 4.61 mum. (C) 2003 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/j.polymer.2003.08.042

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  • Morphology of poly(p-oxybenzoyl) crystal prepared by direct polycondensation of p-hydroxybenzoic acid with p-toluenesulfonyl chloride in pyridine

    K Kimura, T Horii, Y Yamashita

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   41 ( 21 )   3275 - 3282   2003年11月

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    記述言語:英語   出版者・発行元:WILEY-BLACKWELL  

    Poly(p-oxybenzoyl) (POB) crystals were prepared with the reaction-induced crystallization of oligomers during the direct polycondensation of p-hydroxybenzoic acid (HBA) with p-toluenesulfonyl chloride (TsCl) and N,N-dimethylformamide in pyridine. Sheaflike lozenge-shaped POB crystals were obtained, of which the longer diagonal was 7.0-8.0 mum. The influence of the polymerization condition on the morphology was examined to optimize the preparative condition for the crystals exhibiting the clearest habit, and the favorable condition was determined as the molar ratio of TsCl to HBA of 1.3 and polymerization concentration of 3.0%. The crystals possessed extremely high crystallinity and outstanding thermal stability. The formation mechanism of the crystal was proposed as follows. When the number-average degree of polymerization of the oligomers exceeded a critical value of about 4, they were precipitated to form the hexagonal lamellae. The crystals were grown very quickly to lozenge-shaped crystal through screw dislocation with the continuous precipitation of oligomers from the solution. Finally, the further polymerization occurred in the precipitated crystal with developing polymer-chain packing. (C) 2003 Wiley Periodicals, Inc.

    DOI: 10.1002/pola.10916

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  • Self-organizing polycondensation of (E)-4-acetoxycinnamic acid for preparation of poly(p-oxycinnamoyl) microspheres

    K Kimura, H Inoue, SI Kohama, Y Yamashita, Y Sakaguchi

    MACROMOLECULES   36 ( 20 )   7721 - 7729   2003年10月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    Preparation of poly(p-oxycinnamoyl) (POC) microspheres was examined by the reaction-induced phase separation of oligomers during the polycondensation of (E)-4-acetoxycinnamic acid in various solvents. Polymerization in liquid paraffin yielded the microspheres having a smooth surface at 270330 degreesC, of which the average diameter was 4.6 mum. In contrast to this, the morphology of the products was drastically changed in Therm S 800 (TS8) and Therm S 900 (TS9) by polymerization temperature. When the polymerization was carried out at 310 degreesC in TS8 and 300 degreesC in TS9, the microspheres were obtained, of which the average diameter was 3.9 and 3.3 mum, respectively. The platelike crystals were formed under these temperatures, of which thickness was approximately 0.1 mum. The formation of the microspheres was highly related to the miscibility between the oligomers and the solvents. The average diameter of the microspheres increased with the decrease of the miscibility, and this tendency could be accounted for by the interfacial tension between two immiscible liquid phases. The microspheres were formed through the formation of the microdroplets by the liquid-liquid phase separation of the oligomers and the subsequent solidification of the microdroplets due to the further polymerization in them.

    DOI: 10.1021/ma030197q

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  • Morphology control of poly(p-phenylene pyromelliteimide) by means of self-assembling polymerization

    K Kimura, JH Zhuang, K Wakabayashi, Y Yamashita

    MACROMOLECULES   36 ( 17 )   6292 - 6294   2003年8月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    DOI: 10.1021/ma0346761

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  • Preparation of needle-like poly(azomethine) crystals by means of reaction-induced crystallization of oligomers

    K Kimura, JH Zhuang, K Shirabe, Y Yamashita

    POLYMER   44 ( 17 )   4761 - 4764   2003年8月

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    記述言語:英語   出版者・発行元:ELSEVIER SCI LTD  

    Needle-like poly(azomethine) crystals were successfully prepared by the polycondensation of 1,4-phenylenediamine and 1,4-terephthalaldehyde, in liquid paraffin at 180 degreesC. The favorable polymerization concentration for the preparation of the well-defined needle-like crystals was 2.0 x 10(-2) mol l(-1). The average length and width of the needle-like crystals were 7.7 and 0.6 mum, respectively. These crystals possessed high crystallinity and good thermal stability. The extended polymer chains were aligned along the long axis of the needle-like crystal. The morphological observations indicated that the needle-like crystals were formed through the spiral growth of the oligomer lamellae caused by the screw dislocation. (C) 2003 Elsevier Ltd. All rights reserved.

    DOI: 10.1016/S0032-3861(03)00448-8

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  • Novel direct polycondensation of 4-hydroxybenzoic acid by means of reaction-induced crystallization of oligomers under nonstoichiometric condition

    K Kimura, S Kohama, Y Yamashita

    MACROMOLECULES   36 ( 14 )   5043 - 5046   2003年7月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    DOI: 10.1021/ma0258307

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  • Morphology of poly(p-oxybenzoyl) crystals prepared by direct polycondensation of p-hydroxybenzoic acid with diphenyl chlorophosphate

    K Kimura, T Horii, Y Yamashita

    HIGH PERFORMANCE POLYMERS   15 ( 2 )   167 - 179   2003年6月

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    記述言語:英語   出版者・発行元:SAGE PUBLICATIONS LTD  

    We have studied the morphology of poly(p-oxybenzoyl) (POB) crystals prepared by the direct polycondensation of p-hydroxybenzoic acid (HBA) using diphenyl chlorophosphate (DPCP) in the presence of N,N-dimethylformamide. Lozenge-shaped sheaf-like POB crystals were obtained of which the longer diagonal was 16.0-16.5 mum. Favorable polymerization conditions to prepare the crystal exhibiting clear crystal characteristic were the molar ratio of DPCP to HBA of 1.5, the molar ratio of DMF to HBA of 2.6 and the polymerization concentration of 3.0%. The crystals were comprised of low molecular weight polymer of which the degree of polymerization (DPn) was 14 and possessed extremely high crystallinity. The formation mechanism of the crystals was considered by the polymerization time dependences of morphology, yield, density, DPn, crystallite size, and lattice constant as follows. When the DPn of the oligomers exceeded a critical value of about 3, they were precipitated to form the hexagonal lamellae. The lamellae grew very quickly to sheaf-like lozenge-shaped crystal through the screw dislocation with the continuous precipitation of the oligomer from the solution. Finally, further polymerization and the reorganization of polymer chains occurred in the precipitated crystals.

    DOI: 10.1177/0954008303015002002

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  • Self-assembling polycondensation for preparation of poly(p-oxybenzoyl-alt-p-mercaptobenzoyl) whisker

    K Kobashi, K Kimura, Y Yamashita, T Uchida, Y Sakaguchi

    MACROMOLECULES   36 ( 12 )   4268 - 4275   2003年6月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    Self-assembling polycondensation was examined to prepare the whisker of poly(p-oxybenzoyl-alt-p-mereaptobenzoyl). Polymerizations were carried out in liquid paraffin (LPF) and aromatic solvents such as Therm S 800 and 1000 at 300 degreesC for 6 h. Polymerization concentration was 1.0 wt/vol %. The whisker was not obtained by the random copolymerization of p-acetoxybenzoic acid and S-acetyl-4-mercaptobenzoic acid at the molar ratio of 0.5 in feed. However, the whiskers were successfully prepared by the polymerization of S-(4-acetoxybenzoyl)-4-mercaptobenzoic acid (OS) and 4-(S-acetyl-4-mercaptobenzoyl)oxybenzoic acid (SO). The whisker prepared from OS (POS) in LPF was 18 mum in average length and 0.4 mum in average width, and that from SO (PSO) was slightly longer than POS. The whiskers prepared in aromatic solvents were much longer than those in LPF, for which the length was 36-49 mum. These whiskers consist of the alternating polymer chains, and the polymer chains align along the long axis of the whisker. The sequence regularity enhanced the crystallizability of the oligomers, and this led to the formation of whiskers. The oligomer formation rate was much higher than that of transesterfication reaction rate, and this large difference in these two rates made the oligomer precipitate with maintaining the alternating sequence. Further polymerization occurred in the crystals, and the whiskers having the alternating sequence were finally completed. The difference in the two rates increased with the decrease of the miscibility between the oligomer and the solvent, and therefore, OS and LPF were more advantageous to maintain the alternating sequence.

    DOI: 10.1021/ma030046n

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  • Size control of poly(2-oxy-6-naphthoyl) whiskers by the addition of oligomers during polymerization

    AK Sarker, K Kimura, Y Yamashita

    JOURNAL OF APPLIED POLYMER SCIENCE   88 ( 5 )   1320 - 1327   2003年5月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS INC  

    The method of controlling the size of a poly(2-oxy-6-naphthoyl) (PON) whisker was examined with a focus on lengthening the whisker. PON whiskers were prepared by the polymerization of 2-acetoxy-6-naphthoic acid in liquid paraffin at 330degreesC. The whiskers were very symmetrical. and both tips were very sharp. Growth of the whiskers along the length took place by which oligomer lamellae piled up along the long axis of the needlelike crystals with spiral growth. During steady growth until 8 min, the tip angle of the whiskers was constant at 80degrees. However, it became significantly sharper (22degrees) at 30 min, and later the trunk part of the whiskers stopped increasing. To depress the sharpening of the tips and to extend the steady-growth period for longer whiskers, oligomers were added to the polymerization system after 8 min, just before the tip angle became sharper, to keep the concentration of the oligomers in the polymerization system constant. The addition of the oligomers extended the steady-growth period, and the length increased from 12.5 to 17.3 mum. Although the width of the whiskers increased very slightly with the addition of the oligomers, the axial ratio of the whiskers increased from 19.4 to 24.7. (C) 2003 Wiley Periodicals, Inc.

    DOI: 10.1002/app.11816

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  • Dual self-assembling polycondensation of p-acetoxybenzoic acid and p-acetamidobenzoic acid

    K Kimura, K Kobashi, H Maeda, Y Yamashita

    MACROMOLECULAR RAPID COMMUNICATIONS   24 ( 2 )   190 - 193   2003年2月

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    記述言語:英語   出版者・発行元:WILEY-V C H VERLAG GMBH  

    The dual self-assembling polycondensation of p-acetoxybenzoic acid (ABA) and p-acetamidobenzoic acid in Therm S 800 was examined at 300 degreesC. Needle-like crystals and lath-like crystals were formed simultaneously through reaction-induced crystallization of oligomers at a molar ratio of 30-50 mol-% ABA in the feed. The needle-like crystals comprised more p-oxybenzoyl units, whereas the lath-like ones contained higher amounts of p-benzamide moieties.

    DOI: 10.1002/marc.200390032

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  • Influence of solvent on size of poly(p-oxybenzoyl) whiskers prepared from p-acetoxybenzoic acid

    K Kimura, AK Sarker, H Ohmori, Y Yamashita

    JOURNAL OF APPLIED POLYMER SCIENCE   87 ( 7 )   1129 - 1136   2003年2月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS INC  

    Polyp-oxybenzoyl) (POB) crystals are prepared by the polymerization of p-acetoxybenzoic acid (pABA) at 320 degreesC in various solvents to clarify the influence of miscibility between oligomer and solvent on the morphology as well as the size of the crystal. Concerning the morphology, whiskers are formed in less miscible solvents such as liquid paraffin and Barrel process oil B27. On the other hand, bundle-like aggregates of fibrillar crystals tend to be formed in the solvents having higher miscibility such as Therm S 900 and 800, which are aromatic heat exchange media. Further, the solvents having higher temperature at which p-ABA is completely dissolved during polymerization (TS) yield a larger number of the whiskers with smaller width. The higher supersaturation of oligomers in less miscible solvents causes the formation of a larger number of nuclei with smaller size. Bundle-like aggregates are formed in the solvents whose T-s is lower than 140 degreesC by the fibrillation of pillar-like crystals during polymerization owing to the reorganization. This shows a clear relationship between the width and T-s, and between the number of the crystals and T-s. Hence, the size of the whisker such as the length and the width can be predicted by the calculation with Ts, which is very valuable for the preparation of POB whiskers for use as industrial materials. (C) 2002 Wiley Periodicals, Inc.

    DOI: 10.1002/app.11573

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  • 重合誘起型オリゴマー相分離を利用した剛直高分子の高次構造制御

    繊維学会誌   59, 285-289   2003年

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  • 剛直高分子三次元架橋体/ナイロン6複合体の作製とその力学的性質

    繊維学会誌   59(6), 207-212   2003年

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  • Self-assembling polycondensation of 4-aminobenzaldehyde. Preparation of star-like aggregates of cone-shaped poly(azomethine) crystals

    K Kimura, JH Zhuang, M Kida, Y Yamashita, Y Sakaguchi

    POLYMER JOURNAL   35 ( 5 )   455 - 459   2003年

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    記述言語:英語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    DOI: 10.1295/polymj.35.455

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  • Preparation of Aromatic Polyester under Unstoichiometric Condition by Reaction-induced Crystallization of OligomersⅠ - Polymerization of p-Acetoxybenzoic Acid in the presence of Monofunctional compound -

    Macromolecules   35 ( 20 )   7545 - 7552   2002年9月

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  • Size control of poly(p-oxybenzoyl) whiskers by addition of crystals during polymerization of p-acetoxybenzoic

    AK Sarker, K Kimura, S Uchida, Y Yamashita

    HIGH PERFORMANCE POLYMERS   14 ( 2 )   155 - 167   2002年6月

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    記述言語:英語   出版者・発行元:SAGE PUBLICATIONS LTD  

    Control of the size, such as the length and width, of poly(p-oxybenzoyl) (POB) whiskers is a desirable technology. In this study, the addition of nuclei to the polymerization system is examined to control the size of the POB whisker. Polymerizations were carried out in liquid paraffin at 330degreesC for 6 hr The polymerization concentration was 1%. The crystals were prepared for 10 min, of which the tip angle is 80degrees, are added as nuclei to the polymerization solution just before the crystallization is about to begin. The length does not increase at all by addition of the added crystals. The width increases and its distribution becomes significantly broader in all cases. The broadness of the width distribution reveals that nuclei are newly formed in the course of polymerization after the addition of crystals. It is difficult to inhibit the generation of new crystals by the control of the number of added crystals because the precipitation rate of the oligomers is much higher than the consumption rate of the oligomers by crystallization and therefore the excess oligomers which cannot participate in the crystal growth induce nucleation. It is concluded that the addition of the crystals as nuclei is not an available method to lengthen the POB whisker.

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  • Size control of poly(p-oxybenzoyl) whiskers by addition of crystals during polymerization of p-acetoxybenzoic

    AK Sarker, K Kimura, S Uchida, Y Yamashita

    HIGH PERFORMANCE POLYMERS   14 ( 2 )   155 - 167   2002年6月

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    記述言語:英語   出版者・発行元:SAGE PUBLICATIONS LTD  

    Control of the size, such as the length and width, of poly(p-oxybenzoyl) (POB) whiskers is a desirable technology. In this study, the addition of nuclei to the polymerization system is examined to control the size of the POB whisker. Polymerizations were carried out in liquid paraffin at 330degreesC for 6 hr The polymerization concentration was 1%. The crystals were prepared for 10 min, of which the tip angle is 80degrees, are added as nuclei to the polymerization solution just before the crystallization is about to begin. The length does not increase at all by addition of the added crystals. The width increases and its distribution becomes significantly broader in all cases. The broadness of the width distribution reveals that nuclei are newly formed in the course of polymerization after the addition of crystals. It is difficult to inhibit the generation of new crystals by the control of the number of added crystals because the precipitation rate of the oligomers is much higher than the consumption rate of the oligomers by crystallization and therefore the excess oligomers which cannot participate in the crystal growth induce nucleation. It is concluded that the addition of the crystals as nuclei is not an available method to lengthen the POB whisker.

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  • Novel optical oxygen sensing material: metalloporphyrin dispersed in fluorinated poly(aryl ether ketone) films

    Y Amao, Y Tabuchi, Y Yamashita, K Kimura

    EUROPEAN POLYMER JOURNAL   38 ( 4 )   675 - 681   2002年4月

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    記述言語:英語   出版者・発行元:PERGAMON-ELSEVIER SCIENCE LTD  

    A series of new fluorine-containing poly(aryl ether ketone)s (8F-PEKEK(Ar); Ar: 2-2-bis(4-hydroxyphenyl)1.1.1,3,3,3-hexafluoropropane (6FBA), 2,2-bis(4-hydroxyphenyl)pro pane (BA), 2-(4-hydroxyphetiyl)-2-(3-hydroxyphenyl)propane (3.4'-BA) or 9.9'-bis(4-hydroxyphetiyl)fluorine (HF)) are synthesized and applied to the matrix of optical oxygen sensing using phosphorescence quenching of metalloporphyrins, platinum and palladium octaethylporphyrin, (PtOEP and PdOEP) by oxygen. The phosphorescence intensity of PtOEP and PdOEP in 8F-PEKEK(Ar) films decreased with increase of oxygen concentration. The ratio I-0/I-100 is used as a sensitivity of the sensing film. where I-0 and I-100 represent the detected phosphorescence intensities from a film exposed to 100% argon and 100% oxygen, respectively. For PtOEP in 8F-PEKEK(Ar) film. I-0/I-100 values are more than 20.0 and large Stern-Volmer constants more than 0.19%(-1) are obtained compared with PtOEP in polystyrene film. For PdOEP in 8F-PEKEK(Ar) film, on the other hand. the large I-0/I-100 values more than 143 are obtained. However, the Stern-Volmer plots of PdOEP in 8F-PEKEK(Ar) films exhibit considerable linearity at lower oxygen concentration range between 0%. and 20%. These results indicate that PtOEP and PdOEP films are useful optical oxygen sensor at the oxygen concentration range between 0% and 100% and between 0% and 20%, respectively. The response times of PtOEP and PdOEP dispersed in 8F-PEKEK(Ar) films are 5.6 and 3.0 s on going from argon to oxygen and 110.1 and 160.0 s from oxygen to argon, respectively. (C) 2002 Elsevier Science Ltd. All rights reserved.

    DOI: 10.1016/S0014-3057(01)00235-X

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  • 重合反応誘起型オリゴマー結晶化を利用した精密重縮合法の開発

    高分子加工   51, 508-515   2002年

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  • Preparation of Aromatic Polyester under Unstoichiometric Condition by Reaction-induced Crystallization of OligomersⅠ - Polymerization of p-Acetoxybenzoic Acid in the presence of Monofunctional compound -

    Macromolecules   35, 7545-7552   2002年

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  • Preparation of poly(p-oxybenzoyl) whisker in paraffin wax

    AK Sarker, K Kimura, Y Yamashita

    POLYMER JOURNAL   34 ( 6 )   426 - 436   2002年

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    記述言語:英語   出版者・発行元:NATURE PUBLISHING GROUP  

    An influence of solvent on morphology as well as growth mechanism of poly(p-oxybenzoyl) whisker in paraffin wax (PW) was studied comparing with those in liquid paraffin (LPF). Furthermore, the condition for consecutive addition of oligomer was also examined to lengthen the whiskers in PW. Polymerizations of p-acetoxybenzoic acid were carried out in PW and LPF at 330degreesC. Larger number of whiskers having smaller length and width were formed in PW compared with that in LPF. PW was a poorer solvent than LPF and this lower miscibility leaded to the crystallization of lower DPn oligomers. Additionally, formation rate of oligomer was bigger in PW than LPF. These facts resulted in the higher degree of super saturation of oligomers which generated a larger number of nuclei having smaller size. Since the length was determined by the number of nuclei and the yield, the length eventually became shorter. On the basis of the formation mechanism of the whisker in PW, oligomers were added into polymerization system to lengthen the whisker. When oligomers were added to compensate the consumed oligomers while the tip angle was constantly kept at 80degreesC, the steady growth period was expanded and the length increased from 13.4 mum to 22.1 mum.

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  • Preparation of poly(p-oxybenzoyl) whisker in paraffin wax

    AK Sarker, K Kimura, Y Yamashita

    POLYMER JOURNAL   34 ( 6 )   426 - 436   2002年

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    記述言語:英語   出版者・発行元:NATURE PUBLISHING GROUP  

    An influence of solvent on morphology as well as growth mechanism of poly(p-oxybenzoyl) whisker in paraffin wax (PW) was studied comparing with those in liquid paraffin (LPF). Furthermore, the condition for consecutive addition of oligomer was also examined to lengthen the whiskers in PW. Polymerizations of p-acetoxybenzoic acid were carried out in PW and LPF at 330degreesC. Larger number of whiskers having smaller length and width were formed in PW compared with that in LPF. PW was a poorer solvent than LPF and this lower miscibility leaded to the crystallization of lower DPn oligomers. Additionally, formation rate of oligomer was bigger in PW than LPF. These facts resulted in the higher degree of super saturation of oligomers which generated a larger number of nuclei having smaller size. Since the length was determined by the number of nuclei and the yield, the length eventually became shorter. On the basis of the formation mechanism of the whisker in PW, oligomers were added into polymerization system to lengthen the whisker. When oligomers were added to compensate the consumed oligomers while the tip angle was constantly kept at 80degreesC, the steady growth period was expanded and the length increased from 13.4 mum to 22.1 mum.

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  • Polymerization Behavior of poly(ether ketone) via Friedel-Crafts acylation studied by end-group analysis with H-1 NMR

    Y Sakaguchi, K Kimura, M Omori, Y Yamashita

    POLYMER JOURNAL   34 ( 3 )   219 - 224   2002年

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    記述言語:英語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    Polymerization process of poly(ether ketone) made of diphenyl ether (DPE) and isophthaloyl chloride (IPC) catalyzed by aluminum chloride in dichloroethane was characterized by H-1 NMR. The polymerization gave a precipitate of polymer/catalyst complex during the reaction. End-group analyses for polymer appeared as precipitate and oligomers stayed in the solution were carried out respectively after decomposition of the complex by treatment with methanol. Time dependence of the content of end groups showed that the oligomer of which molecular weight exceeded a critical value precipitated out independent of the functionality of the end groups, and further reaction proceeded in the precipitate as well as in the solution. Another approach to understand the reaction was carried out by direct H-1 NMR observation of the polymerization in an NMR sample tube. This experiment detected the molecular weight change of soluble oligomer in the reaction system at real time, and the results were consistent with those of isolated oligomers described above.

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  • Synthesis of thermally cross-linkable fluorine-containing poly(aryl ether ketone)s I. Phenylethynyl terminated poly(aryl ether ketone)s

    K Kimura, A Nishichi, Y Yamashita

    POLYMER JOURNAL   34 ( 3 )   209 - 218   2002年

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    記述言語:英語   出版者・発行元:NATURE PUBLISHING GROUP  

    Fluorine-containing poly(aryl ether ketone)s (PEKs) derived from 2,3,4,5,6-pentafluorobenzoic acid (PFBA) exhibit outstanding solubility, thermal stability, low dielectric constant, low moisture absorption and high transparency. Hence, they are expected to be available for optical and electric materials. In such applications, excellent solubility is of great advantage for making thin film and coating. Contrary to this advantage, this is of disadvantage from a point of solvent resistance. Thermally cross-linkable fluorine-containing PEKs terminated with phenylethynyl moiety (PEK-PEP) are synthesized to improve the solvent resistance in this study. Cross-linking reaction occurs over 320degreesC and it brings about not only the outstanding solvent resistance but also the increase of T, Relationship between the cross-linking density and T, can be fundamentally interpreted by configurational entropy theory. Furthermore, the cured PEK-PEPs possess excellent thermal stability with the 10% weight loss temperature in the range from 544 to 598degreesC.

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  • Polymerization Behavior of poly(ether ketone) via Friedel-Crafts acylation studied by end-group analysis with H-1 NMR

    Y Sakaguchi, K Kimura, M Omori, Y Yamashita

    POLYMER JOURNAL   34 ( 3 )   219 - 224   2002年

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    記述言語:英語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    Polymerization process of poly(ether ketone) made of diphenyl ether (DPE) and isophthaloyl chloride (IPC) catalyzed by aluminum chloride in dichloroethane was characterized by H-1 NMR. The polymerization gave a precipitate of polymer/catalyst complex during the reaction. End-group analyses for polymer appeared as precipitate and oligomers stayed in the solution were carried out respectively after decomposition of the complex by treatment with methanol. Time dependence of the content of end groups showed that the oligomer of which molecular weight exceeded a critical value precipitated out independent of the functionality of the end groups, and further reaction proceeded in the precipitate as well as in the solution. Another approach to understand the reaction was carried out by direct H-1 NMR observation of the polymerization in an NMR sample tube. This experiment detected the molecular weight change of soluble oligomer in the reaction system at real time, and the results were consistent with those of isolated oligomers described above.

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  • Synthesis of thermally cross-linkable fluorine-containing poly(aryl ether ketone)s I. Phenylethynyl terminated poly(aryl ether ketone)s

    K Kimura, A Nishichi, Y Yamashita

    POLYMER JOURNAL   34 ( 3 )   209 - 218   2002年

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    記述言語:英語   出版者・発行元:NATURE PUBLISHING GROUP  

    Fluorine-containing poly(aryl ether ketone)s (PEKs) derived from 2,3,4,5,6-pentafluorobenzoic acid (PFBA) exhibit outstanding solubility, thermal stability, low dielectric constant, low moisture absorption and high transparency. Hence, they are expected to be available for optical and electric materials. In such applications, excellent solubility is of great advantage for making thin film and coating. Contrary to this advantage, this is of disadvantage from a point of solvent resistance. Thermally cross-linkable fluorine-containing PEKs terminated with phenylethynyl moiety (PEK-PEP) are synthesized to improve the solvent resistance in this study. Cross-linking reaction occurs over 320degreesC and it brings about not only the outstanding solvent resistance but also the increase of T, Relationship between the cross-linking density and T, can be fundamentally interpreted by configurational entropy theory. Furthermore, the cured PEK-PEPs possess excellent thermal stability with the 10% weight loss temperature in the range from 544 to 598degreesC.

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  • Control of the length of aromatic polyester whiskers

    A. K. Sarker, K. Kimura, F. Yokoyama, Y. Yamashita

    High Performance Polymers   13 ( 2 )   S351 - S364   2001年6月

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    記述言語:英語  

    The control method of poly(p-oxybenzoyl) (POB) whisker length is reported, with the main focus being on how to make the length of the whiskers longer. The POB whiskers were prepared by the polymerization of p-acetoxybenzoic acid in LPF ar 330°C. The increase in whisker length is caused by the way oligomer lamellae pile up along the long axis of the needle-like crystals with spiral growth. From the present detailed morphological observations during polymerization, the tip angle of the whiskers is constant at 80° up to a time 10 min, whereas it becomes significantly sharper to 12° at 30 min. This sharpening of the tip angles seems to be highly related to the degree of supersaturation of the oligomers dissolved in solution. In order to depress the sharpening of the tip angle and to extend the steady-state growth for increase of the whisker length, oligomers were added twice into the polymerization system, after 10 min just before the tip angle becomes sharper and then after 20 min. The addition of oligomers extended the steady-state growth period, and the length was increased from 40 μm to 47 μm with the first addition and then to 50 μm with the second addition. The addition of oligomers during steady-state growth gives the most favourable conditions for continuous growth with spiral growth.

    DOI: 10.1088/0954-0083/13/2/330

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  • Polymerization behaviors of poly(ether ketone) via Friedel-Crafts acylation.

    Y Sakaguchi, K Kimura, M Omori, Y Yamashita

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   221   U303 - U303   2001年4月

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    記述言語:英語   掲載種別:研究発表ペーパー・要旨(国際会議)   出版者・発行元:AMER CHEMICAL SOC  

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  • Whisker of poly(p-oxybenzoyl-alt-mercaptobenzoyl).

    K Kimura, Y Yamashita, K Kobashi, Y Sakaguchi

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   221   U311 - U311   2001年4月

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    記述言語:英語   掲載種別:研究発表ペーパー・要旨(国際会議)   出版者・発行元:AMER CHEMICAL SOC  

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  • フッ素原子含有芳香族ポリマー群の開発

    高分子加工   50, 314-321   2001年

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  • Synthesis of novel fluorine-containing poly(aryl ether nitrile)s derived from 2,3,4,5,6-pentafluorobenzonitrile

    K Kimura, Y Tabuchi, A Nishichi, Y Yamashita, Y Okumura, Y Sakaguchi

    POLYMER JOURNAL   33 ( 3 )   290 - 296   2001年

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    記述言語:英語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    2,3,4,5,6-Pentafluorobenzonitrile (PFBN) is a valuable intermediate and it is available as a commercial product. In this paper, synthesis and characterization of novel fluorinated poly(ether nitrile)s (PEN) derived from PFBN is reported. Novel fluorinated PENs containing fluorine atoms in the main chain and pendant phenoxy group (2F-PEN) are synthesized by aromatic nucleophilic substitution reaction, of which M-n ranges from 1.77 x 10(4) to 5.16 x 10(4). The obtained PENs show excellent solubilities in common solvents, and BF-PEN(6FBA) and 2F-PEN(DPE) can be cast as tough transparent films. These polymers have high thermal stabilities with the 5% weight loss temperature in the range 509-562 degreesC and the T-g of 142-235 degreesC, which is highly dependent on the structures.

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  • Synthesis of novel fluorine-containing poly(aryl ether nitrile)s derived from 2,3,4,5,6-pentafluorobenzonitrile

    K Kimura, Y Tabuchi, A Nishichi, Y Yamashita, Y Okumura, Y Sakaguchi

    POLYMER JOURNAL   33 ( 3 )   290 - 296   2001年

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    記述言語:英語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

    2,3,4,5,6-Pentafluorobenzonitrile (PFBN) is a valuable intermediate and it is available as a commercial product. In this paper, synthesis and characterization of novel fluorinated poly(ether nitrile)s (PEN) derived from PFBN is reported. Novel fluorinated PENs containing fluorine atoms in the main chain and pendant phenoxy group (2F-PEN) are synthesized by aromatic nucleophilic substitution reaction, of which M-n ranges from 1.77 x 10(4) to 5.16 x 10(4). The obtained PENs show excellent solubilities in common solvents, and BF-PEN(6FBA) and 2F-PEN(DPE) can be cast as tough transparent films. These polymers have high thermal stabilities with the 5% weight loss temperature in the range 509-562 degreesC and the T-g of 142-235 degreesC, which is highly dependent on the structures.

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  • Whisker of poly(p-oxybenzoyl-co-p-mercaptobenzoyl) - Influence of sequence on polymer morphology

    K Kimura, D Nakajima, K Kobashi, Y Yamashita, F Yokoyama, T Uchida, Y Sakaguchi

    POLYMERS FOR ADVANCED TECHNOLOGIES   11 ( 8-12 )   747 - 756   2000年8月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS LTD  

    Aromatic polymers are expected to possess outstanding properties. However in many cases they do not show good processability because of their chain regidity. We have been studying the morphology control of rigid polymers during polymerization to overcome this problem and succeeded in preparing the whiskers of poly (p-oxybenzoyl) and poly (p-mercaptobenzoyl) by the polymerization in liquid paraffin at around 300 degreesC. These whiskers are formed by the reaction induced crystallization of oligomers during solution polymerization.
    The preparation of copolymer whiskers is very interesting to design the new materials which are endowed with novel functions. The aim of this study is to prepare the whisker of poly (p-oxybenzoyl-co-p-mercaptobenzoyl) and to clarify the influence of the copolymerization on the morphology, especially focusing on the sequence regularity. The introduction of comonomer unit into polymer chain structure extinguishes the crystal habit due to the lower crystallizability and the whiskers can be obtained by the random copolymerization of 4-acetoxybenzoic acid (ABA) and S-acetyl-4-mercaptobenzoic acid (AMBA) only when chi (f) (the molar ratio of ABA/AMBA in feed) is 1.0-0.7 and 0.05-0. However, the copolymer whiskers are obtained by the polymerization of OS, OOS and SSO monomers which produce the alternating and periodic copolymers. These copolymer whiskers consist of the alternating or periodic copolymer chains and their chains align along the long axis of the whisker. The sequence regularity enhances the crystal lizability of cooligomers and this lends to the formation of the whiskers. The sequence regularity in copolymers is a very influential parameter to control the morphology and the copolymer whiskers can be prepared by giving the regular sequences. Copyright (C) 2000 John Wiley & Sons, Ltd.

    DOI: 10.1002/1099-1581(200008/12)11:8/12<747::AID-PAT53>3.0.CO;2-4

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  • Synthesis of novel fluorine-containing poly(aryl ether ketone)s

    K Kimura, Y Tabuchi, Y Yamashita, PE Cassidy, JW Fitch, Y Okumura

    POLYMERS FOR ADVANCED TECHNOLOGIES   11 ( 8-12 )   757 - 765   2000年8月

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    記述言語:英語   出版者・発行元:JOHN WILEY & SONS LTD  

    The high-performance fluorinated polymers have been receiving considerable attention as interesting advanced materials. The incorporation of fluorine atoms into polymer chains leads to polymers with increased solubility, flame resistance, thermal stability and glass transition temperature while also leading to decreased color crystallinity, dielectric constant and moisture absorption. 2,3,4,5,6-Pentafluorobenzoic acid (PFBA) is a valuable intermediate for pharmaceuticals, pesticides, perfumes, cosmetics and so on, and it is available as a commercial product. However, the polymers derived from PFBA have not been reported so far. In this paper, we report the synthesis and characterization of novel fluorinated poly(aryl ether ketone)s (PEKs) containing 2,3,5,6-tetrafluoro-1,4-phenylene moieties derived from PFBA. Novel fluorinated PEKs are prepared from PFBA by aromatic nucleophilic substitution reaction, of which M-n values range from 2.28 x 10(4) to 1.04 x 10(5). They have all para connected linear structures. The aromatic fluorine of the para position to the carbonyl groups of monomers is preferentially substituted by phenoxide and this para orientation is mainly attributed to the steric effect rather than pi -electron density. The obtained PEKs except 8F-PEKEK (BP) show excellent solubilities in common solvents and can be cast into tough transparent films. They also exhibit high glass transition temperatures depending on the structures and outstanding thermal stabilities. Furthermore, these fluorine-containing PEKs exhibit low dielectric constants from 2.87 to 3.52 at I MHz. Copyright (C) 2000 John Wiley & Sons, Ltd.

    DOI: 10.1002/1099-1581(200008/12)11:8/12<757::AID-PAT54>3.0.CO;2-Z

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  • Morphology control of aromatic polymers by fluorinated end groups.

    K Kimura, H Ohmori, F Yokoyama, Y Yamashita

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   216   U136 - U136   1998年8月

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    記述言語:英語   掲載種別:研究発表ペーパー・要旨(国際会議)   出版者・発行元:AMER CHEMICAL SOC  

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  • Copolymerization effect of m-acetoxybenzoic acid on morphology of poly(oxy-1,4-benzenediylcarbonyl) whiskers

    Kunio Kimura, Yuhiko Yamashita

    Journal of Polymer Science, Part A: Polymer Chemistry   34 ( 5 )   739 - 745   1996年4月

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    記述言語:英語   出版者・発行元:John Wiley and Sons Inc.  

    Copolymerizations of p-acetoxybenzoic acid (p-ABA) and m-acetoxybenzoic acid (m-ABA) were carried out in liquid paraffin at 330°C without stirring. Needlelike crystals are obtained when the content of m-ABA in the feed (χf) is in the range of 0-30 mol %. These needlelike crystals are inclined to show the fibrillation in both ends and the radial growth nature from the central part as χf increased. At higher χf than 40 mol %, crystals are not precipitated during polymerization. The content of m-oxybenzoyl units in the obtained whiskers (χw) are much lower than χf. The details of the polymerization and crystallization processes reveal that cooligomers containing more m-oxybenzoyl units cannot participate in the formation of needlelike crystals due to the higher solubility and the segregation effect of crystallization. The whiskers are predominantly formed by co-oligomers consisting almost entirely of p-oxybenzoyl units. © 1996 John Wiley &amp
    Sons, Inc.

    DOI: 10.1002/(SICI)1099-0518(19960415)34:5<739::AID-POLA3>3.0.CO;2-I

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  • Morphology Control of Aromatic Polymers during Polymerization

    Journal of The Fawlty of Enuironmeutal Scieuce and Technology Okayama University   1 ( 1 )   221 - 228   1996年

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  • 重合過程を利用した芳香族高分子の高次構造形成

    岡山大学環境理工学部研究報告   1 ( 1 )   221 - 228   1996年

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  • Whisker of Rigid-rod Polymers

    Polymeric Material Encyclopedia   8707 - 8713   1996年

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  • Poly(benjobisthiajole-imide)s

    Polymeric Material Encyclopedia   5638 - 5641   1996年

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  • FORMATION MECHANISM OF POLY(4'-OXY-4-BIPHENYLCARBONYL) CRYSTALS OBTAINED BY SOLUTION POLYMERIZATION

    K KIMURA, S ENDO, Y KATO, T INABA, Y YAMASHITA

    MACROMOLECULES   28 ( 1 )   255 - 259   1995年1月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    Poly(4'-oxy-4-biphenylcarbonyl) (POBP) crystals are obtained from 4'-acetoxybiphenyl-4-carboxylic acid by high-temperature solution polycondensation. When the polymerization is carried out in aromatic solvents such as Therm S 800 and Therm S 900, bundlelike aggregates of fibrillar crystals are obtained. Their length and width are 5-10 and 0.1-0.2 mu m. These fibrillar crystals are linked laterally to one another at the central part. The electron diffraction experiments reveal that the polymer chains align along the long axis of the fibrillar crystals. From terphenyl are obtained hexagonal slablike crystals, of which the thickness is 2-3 mu m and the width is on the average 10 mu m. These slablike crystals are also fibrillated in the direction of the thickness. The formation mechanism of the fibrillar crystals was followed by the observation of the crystal morphology and the polymerization time dependencies of the yield of the crystals, the crystal sizes, and the degree of polymerization (DP). Scanning electron microscopic observation of incipient crystals obtained after 1 h showed convex-lens-like shape. Transmission electron microscopic observation of them showed the lamellar steps due to spiral growth at their thin edge. The morphological observation of the crystals obtained after 2 h showed lenslike shape but many protrusions with a width of 0.1-0.2 mu m in their surfaces. This result indicates that the reorganization of crystals is accompanied by an increase of the DP by postpolymerization. From these experimental facts, it can be deduced that the formation mechanism of the bundlelike aggregates of fibrillar crystals is fundamentally similar to that in poly(oxy-1,4-benzenediylcarbonyl) whiskers and the apparent difference in crystal morphology is caused by the reorganization of crystals during slow lamellar crystallization of oligomers formed in solution polymerization.

    DOI: 10.1021/ma00105a033

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  • SYNTHESIS AND CHARACTERIZATION OF THERMOTROPIC POLY(BENZOBISTHIAZOLE)S

    K KIMURA, DL MEURER, RF HUTZLER, JW FITCH, PE CASSIDY

    MACROMOLECULES   27 ( 6 )   1303 - 1306   1994年3月

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    記述言語:英語   出版者・発行元:AMER CHEMICAL SOC  

    Thermotropic polymers containing the benzo[1,2-d:4,5-d]bisthiazole-2,6-diyl unit combined with 2,5-bis(n-alkoxy)-1,4-phenylene (Cn-PTBT) or 5-(alkyloxy)-1,3-phenylene units (Cn-PIBT) were synthesized via precursor polyamides prepared by low-temperature solution polycondensation. The polyamides were converted into Cn-PTBT or Cn-PIBT by heating at 250-degrees-C. All polymers except for one containing 2,5-bis(n-butyloxy)-1,4-phenylene showed anisotropic melt phases in the range of 280-450-degrees-C. Characterization of these polymers by differential scanning calorimetry, thermal optical analysis, X-ray diffraction, and thermogravimetric analysis is reported. The polymers were not stable at high temperatures due to decomposition of the alkyloxy side chains.

    DOI: 10.1021/ma00084a003

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  • SYNTHESIS AND CHARACTERIZATION OF NOVEL POLY(BENZOBISTHIAZOLE-IMIDE)S

    K KIMURA

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   32 ( 1 )   181 - 185   1994年1月

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    記述言語:英語   掲載種別:記事・総説・解説・論説等(学術雑誌)   出版者・発行元:JOHN WILEY & SONS INC  

    DOI: 10.1002/pola.1994.080320121

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  • Synthesis and characterization of poly(p-phenylene terephthalate) crystals obtained by crystallization during polymerization

    K. Kimura, S. Endo, Y. Kato, Y. Yamashita

    High Performance Polymers   6 ( 1 )   83 - 93   1994年

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  • SOLVENT EFFECT ON THE MORPHOLOGY OF POLY(OXY-L,4-BENZENEDIYLCARBONYL) WHISKERS FROM P-ACETOXYBENZOIC ACID

    K KIMURA, S ENDO, Y KATO, Y YAMASHITA

    POLYMER   35 ( 1 )   123 - 127   1994年

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    記述言語:英語   出版者・発行元:ELSEVIER SCI LTD  

    Poly(oxy-1,4-benzenediylcarbonyl) (POB) whiskers from p-acetoxybenzoic acid were prepared in mixtures of liquid paraffin having many branched carbons (LP) and completely linear paraffin (SW). The crystal shapes of the POB whiskers obtained were largely changed by the mixing ratio of LP and SW. When the content of SW in the solvents increased: (i) both the length and the width of the whiskers decreased; (ii) the tip angle of the whiskers increased; and (iii) radial growth of the whiskers increased. The size of the POB whiskers was attributed to both the number and the size of those lamellar crystals with screw dislocations (primary nuclei for whisker growth) which had formed in the early stages of polymerization. In SW, larger numbers of smaller lamellar crystals were formed than in LP, owing to the lower solubility of POB oligomers at 330 degrees C in SW; that is, the higher supersaturated state of the POB oligomers produced a larger number of smaller primary nuclei for whisker growth. Hence, whiskers having smaller lengths and widths were obtained as the content of SW increased. The other characteristic changes in whisker shapes, i.e. tip angles and radial growth, also seemed to be attributable to the degree of supersaturation of the POB oligomers, though further study is required. The thermal properties of the whiskers were evaluated by differential scanning calorimetry and thermogravimetric analysis.

    DOI: 10.1016/0032-3861(94)90059-0

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  • Morphology and Formation Mechanism of Poly(4-oxy-4-biphenylcarbonyl)Crystals obtained by Solution Polymerization (共著)

    ISF'94 PROCEEOING OF THE INTERNATIONAL SYMPOSIUM ON FIBER SCIENCE AND TECHNOLOGY   309   1994年

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  • Crystallization of Copolymer of Poly(oxy-1,4-benzenediylcarbonyl) with m-Acetoxybenzoic acid during Solution Polymerization (共著)

    ISF'94 PROCEEOING OF THE INTERNATIONAL SYMPOSIUM ON FIBER SCIENCE AND TECHNOLOGY   344   1994年

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  • SYNTHESIS AND CHARACTERIZATION OF POLY(4-MERCAPTOBENZOYL) WHISKERS FROM S-ACETYL-4-MERCAPTOBENZOIC ACID

    K KIMURA, Y YAMAMSHITA

    POLYMER   35 ( 15 )   3311 - 3316   1994年

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    記述言語:英語   出版者・発行元:ELSEVIER SCI LTD  

    Poly(4-mercaptobenzoyl) (PMB) whiskers were obtained from S-acetyl-4-mercaptobenzoic acid by high-temperature solution polymerization. The whisker prepared in liquid paraffin at a concentration of 1.0% at 300-degrees-C has an almost uniform width of 0.3-0.5 mum and a length of 5-8 mum. These whiskers show radial growth from the centre. The optimal conditions for preparing them are by using liquid paraffin as a solvent and polymerization temperatures of 260-300-degrees-C. Electron diffraction reveals that the PMB whiskers show single crystal nature and the polymer chains are aligned along the long axis of the whisker. D.s.c. analysis of the PMB whiskers shows the presence of the reversible solid-solid transition as already reported by Kricheldorf et al. The transition temperature and enthalpy of the PMB whiskers are higher and larger than those of PMB crystals with other morphologies. Another endotherm is found at approximately 420-degrees-C, but only when measurement is carried out using a faster heating rate of 100-degrees-C min-1. This is deduced to be a solid-liquid crystal transition from the observation of the nematic domain structure in a quenched specimen using an optical microscope. Finally, the formation mechanism of the PMB whiskers is discussed from the polymerization time dependencies of the length, the degree of polymerization and the yield.

    DOI: 10.1016/0032-3861(94)90140-6

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  • Copolymerization Effects of m-Acetoxybenzoic acid in the Morphology of Poly(oxy-1,4-benzenediyl carbonyl) Whiskers (共著)

    35th IVPAC International Symposium on Macromolecules Abstracts   35   430   1994年

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  • 高分子ウィスカーの形状制御とその可能性(共著)

    ポリファイル   30 ( 357 )   20 - 22   1993年

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  • SYNTHESIS AND CHARACTERIZATION OF POLY(OXY-2,6-NAPHTHALENEDIYLCARBONYL) WHISKERS FROM 2-ACETOXY-6-NAPHTHOIC ACID

    K KIMURA, S ENDO, Y KATO, Y YAMASHITA

    POLYMER   34 ( 5 )   1054 - 1059   1993年

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    記述言語:英語   出版者・発行元:ELSEVIER SCI LTD  

    The synthesis and characterization of poly(oxy-2,6-naphthalenediylcarbonyl) (PON) whiskers from 2-acetoxy-6-naphthoic acid are described. The important factors in controlling PON crystal morphologies during high-temperature solution polymerization are polarity of solvent, concentration of monomer and stirring. Less-polar solvents like liquid paraffin or Therm S 800, low concentration of monomer and no stirring are desirable for making PON whiskers. The size of the whisker prepared in liquid paraffin is 7-17 mum in length and 0.5-1.0 mum in width. From its electron diffraction patterns, it was found that this whisker exhibits a single-crystal nature and the polymer chains align along the long axis of the whisker. Owing to the close packing of polymer chains in this crystal, the whisker has the highest thermal stability compared with the other fibrillar and slab-like crystals. The formation mechanism of PON whiskers is also investigated in comparison to that of poly(oxy-1,4-benzenediylcarbonyl) whiskers.

    DOI: 10.1016/0032-3861(93)90229-4

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  • Morphology Control of Polymer Whiskers

    Polyfile   30 ( 357 )   20 - 22   1993年

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  • Synthesis and Characterization of Polybenzazoles Containing Hexa fluoroisopropylidene (共著)

    High Performance Polymers   4 ( 3 )   161 - 171   1992年

  • STUDIES ON MORPHOLOGY CONTROL OF POLYMER CRYSTALS DURING POLYMERIZATION .4. MOLECULAR-WEIGHT CHANGE DURING POLY(PARA-OXYBENZOYL) WHISKER FORMATION

    Y KATO, Y YAMASHITA, K KIMURA, S ENDO, T OHTA

    KOBUNSHI RONBUNSHU   47 ( 7 )   583 - 589   1990年

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    記述言語:日本語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

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  • ポリ(p-オシシベンゾイル)ウィスカーの生成過程における重合度変化(共著)

    高分子論文集   47 ( 7 )   583 - 589   1990年

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    記述言語:英語  

    DOI: 10.1295/koron.47.583

    Scopus

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  • SHAPE CHANGE OF POLY(PARA-OXYBENZOYL) WHISKERS FORMED DURING THE SOLUTION POLYMERIZATION

    Y KATO, Y YAMASHITA, K KIMURA, S ENDO, K KAJISAKI

    KOBUNSHI RONBUNSHU   45 ( 12 )   973 - 978   1988年

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    記述言語:日本語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

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  • ポリ(p-オシシベンゾイル)ウィスカーの生成過程における形状変化(共著)

    高分子論文集   45 ( 12 )   973 - 978   1988年

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  • Preparation and Formation of Poly(oxycarbonyl-1.4-pyeny lene) Whiskers from 4-acetoxy benzoic Acid (共著)

    Makromolecular Chemie, Rapid Communication   9 ( 10 )   687 - 691   1988年

  • STUDIES ON MORPHOLOGY CONTROL OF POLYMER CRYSTALS DURING POLYMERIZATION .1. PREPARATION OF POLY(P-OXYBENZOYL) WHISKERS

    Y KATO, S ENDO, K KIMURA, Y YAMASHITA, H TSUGITA, K MONOBE

    KOBUNSHI RONBUNSHU   44 ( 1 )   35 - 39   1987年

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    記述言語:日本語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

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  • ポリ(p-オキシベンゾイル)ウィスカーの調製(共著)

    高分子論文集   44 ( 1 )   35 - 39   1987年

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  • ポリ(p-オキシベンゾイル)ウィスカーの生成機構(共著)

    高分子論文集   44 ( 1 )   41 - 44   1987年

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  • STUDIES ON MORPHOLOGY CONTROL OF POLYMER CRYSTALS DURING POLYMERIZATION .2. FORMATION MECHANISM OF POLY(P-OXYBENZOYL) WHISKERS

    Y YAMASHITA, Y KATO, S ENDO, K KIMURA, H TSUGITA, K MONOBE

    KOBUNSHI RONBUNSHU   44 ( 1 )   41 - 44   1987年

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    記述言語:日本語   出版者・発行元:SOC POLYMER SCIENCE JAPAN  

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  • Poly(p-oxybenzoyl)whiskers (共著)

    31st IVPAC Makromolecular Symposium Abstracts   31 ( 4 )   187   1987年

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講演・口頭発表等

  • 環状ポリエチレンと直鎖状または星型ポリエチレンのブレンド系における流動場結晶化

    岡田 大輝, 小林 慧子, 山崎 慎一, 新 史紀, 木村 邦生

    2021年繊維学会秋季研究発表会  2021年11月19日 

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  • 重合相変化を利⽤したアラミド中空微粒⼦のサイズと空孔率制御

    中山 博文, 木林 直人, 新 史紀, 山崎 慎一, 木村 邦生

    2021年繊維学会秋季研究発表会  2021年11月18日 

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  • 重合結晶化を利⽤したポリバニリン酸針状結晶の調製

    西村 周平, 新 史紀, 山崎 慎一, 木村 邦生

    2021年繊維学会秋季研究発表会  2021年11月18日 

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  • ディンプル型球状微粒⼦の形態制御

    新 史紀, 池田 侑季子, 松田 敬裕, 山崎 慎一, 木村 邦生

    2021年繊維学会秋季研究発表会  2021年11月18日 

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  • 環状と直鎖状ポリエチレンブレンド系の引張過程における応力ひずみ挙動の変化

    栗本 将成, 新 史紀, 山崎 慎一, 木村 邦生

    第36回中国四国地区高分子若手研究会  2021年11月4日 

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  • 重合結晶化によるポリ(p-オキシシンナモイル)の選択的調製

    宮脇 里奈, 新 史紀, 山崎 慎一, 木村 邦生

    第36回中国四国地区高分子若手研究会  2021年11月4日 

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  • ポリ(p-ジオキサノン)のバンド球晶生成における結晶化温度及び分子量依存性

    木村 茉由子, 山崎 慎一, 新 史紀, 木村 邦生

    第70回高分子討論会  2021年9月7日 

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  • 環拡大重合による環状ポリ(p-ジオキサノン)の合成と球晶成長

    大野 良悟, 山崎 慎一, 新 史紀, 木村 邦生

    第70回高分子討論会  2021年9月6日 

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  • ポリ(ε-カプロラクトン)及びポリ(p-ジオキサノン)でグラフト化されたセルロースナノ結晶の結晶化核剤能の評価

    馬杉 直樹, 小林 慧子, 大村 雅也, 新 史紀, 山崎 慎一, 木村 邦生

    第35回中国四国地区高分子若手研究会  2020年11月6日 

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  • 側鎖にイソブチル基を有する新規ポリオレフィンの合成と結晶化

    奥泉 陶和, 新 史紀, 山崎 慎一, 木村 邦生

    第35回中国四国地区高分子若手研究会  2020年11月5日 

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  • 鎖の中央に構造欠陥を有するポリ(ε-カプロラクトン)の合成と結晶化

    安東 眞矢, 新 史紀, 山崎 慎一, 木村 邦生

    第35回中国四国地区高分子若手研究会  2020年11月5日 

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  • 分子量が異なるパーフルオロデシル基を有するテレケリックポリエチレンの 結晶化及び表面物性

    藤後 友輔, 新 史紀, 山崎 慎一, 木村 邦生

    第35回中国四国地区高分子若手研究会  2020年11月5日 

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  • AB2型モノマーであるカフェ酸を原料とした高分子合成とその一次構造解析

    新 史紀, 河田 駿也, 山崎 慎一, 木村 邦生

    2020年度繊維学会年次大会  2020年6月12日 

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  • ポリ(アミド-イミド)ウィスカーの調製

    藤原 響美, 新 史紀, 山崎 慎一, 木村 邦生, 内田 哲也

    2020年度繊維学会年次大会  2020年6月12日 

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  • 高分子鎖の中央にトリアゾール環を有するポリ(ε-カプロラクトン)の合成と結晶化

    安東 眞矢, 新 史紀, 山崎 慎一, 木村 邦生

    第69回高分子学会年次大会  2020年5月27日 

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  • 分子量が異なる両末端にパーフルオロアルキル基を有するテレケリックポリエチレンの結晶化挙動および表面物性

    藤後 友輔, 新 史紀, 山崎 慎一, 木村 邦生

    第69回高分子学会年次大会  2020年5月27日 

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  • ポリジオキサノンおよびその共重合体の合成とそれらの流動誘起結晶化と分解挙動

    林 章裕, 木村 邦生, 山崎 慎一, 新 史紀

    日本化学会第100春季年会  2020年3月22日 

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Works(作品等)

  • Development of new polymers having irradiation stability

    1999年

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  • 耐放射線性高分子材料の開発

    1999年

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受賞

  • 繊維学会賞

    2003年  

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    受賞国:日本国

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共同研究・競争的資金等の研究

  • 精密重縮合技術の開発

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    資金種別:競争的資金

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  • 高性能高分子の高次構造制御

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    資金種別:競争的資金

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  • 新規高性能高分子の合成

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    資金種別:競争的資金

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  • New methodology for precision polycondensation

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    資金種別:競争的資金

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  • Morphology control of high performance polymers

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    資金種別:競争的資金

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  • Synthesis of Novel high performance polymers

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    資金種別:競争的資金

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担当授業科目

  • Introduction to Environmental Chemistry (2021年度) 第1学期  - 木1,木2

  • 有機化学Ⅳ (2021年度) 第1学期  - 金3~4

  • 有機化学Ⅴ (2021年度) 第2学期  - 火3~4

  • 有機化学III (2021年度) 1・2学期  - [第1学期]金3~4, [第2学期]火3~4

  • 特別研究 (2021年度) 通年  - その他

  • 現代の化学 (2021年度) 第3学期  - 金1~3

  • 現代の化学 (2021年度) 第3学期  - 金1~3

  • 現代化学入門 (2021年度) 3・4学期  - 火9

  • 環境化学概論 (2021年度) 第1学期  - 木1~2

  • 環境調和高分子合成論 (2021年度) 後期  - 月3~4

  • 環境高分子材料学演習 (2021年度) 前期  - その他

  • 環境高分子材料学演習 (2021年度) 前期  - その他

  • 環境高分子材料学演習 (2021年度) 後期  - その他

  • 環境高分子材料学演習 (2021年度) 後期  - その他

  • 省エネルギー精密重合論 (2021年度) 前期  - その他

  • 高分子化学Ⅱ (2021年度) 第3学期  - 木3~4

  • 高分子化学I (2021年度) 第1学期  - 火3~4

  • 高分子化学I (2021年度) 1~3学期  - [第1学期]火3~4, [第2学期]その他, [第3学期]木3~4

  • 高分子化学I (2021年度) 1~3学期  - [第1学期]火3~4, [第2学期]その他, [第3学期]木3~4

  • Advances in Material and Energy Science (2020年度) 夏季集中  - その他

  • Introduction to Environmental Chemistry (2020年度) 第1学期  - 木1,木2

  • 有機化学Ⅳ (2020年度) 第1学期  - 金4,金5

  • 有機化学Ⅴ (2020年度) 第2学期  - 火2,火3

  • 有機化学III (2020年度) 1・2学期  - [第1学期]金4,金5, [第2学期]火2,火3

  • 特別研究 (2020年度) 通年  - その他

  • 現代の化学 (2020年度) 第3学期  - 金1,金2,金3

  • 現代の化学 (2020年度) 第3学期  - 金1,金2,金3

  • 現代の化学 (2020年度) 第3学期  - 金1,金2,金3

  • 現代化学入門 (2020年度) 3・4学期  - 火9

  • 環境化学概論 (2020年度) 第1学期  - 木1,木2

  • 環境調和高分子合成論 (2020年度) 後期  - 月2,月3

  • 環境高分子材料学演習 (2020年度) 前期  - その他

  • 環境高分子材料学演習 (2020年度) 後期  - その他

  • 環境高分子材料学演習 (2020年度) 後期  - その他

  • 環境高分子材料学演習 (2020年度) 前期  - その他

  • 省エネルギー精密重合論 (2020年度) 前期  - その他

  • 高分子化学Ⅱ (2020年度) 第3学期  - 木2,木3

  • 高分子化学I (2020年度) 第1学期  - 火2,火3

  • 高分子化学I (2020年度) 1~3学期  - [第1学期]火2,火3, [第2学期]その他, [第3学期]木2,木3

  • 高分子化学I (2020年度) 第1学期  - 火2,火3

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