Updated on 2024/02/01

写真a

 
KIMURA Kunio
 
Organization
Faculty of Environmental, Life, Natural Science and Technology Professor
Position
Professor
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Degree

  • Crystallization of Aromatic Polymers during solution Polymerization ( Osaka University )

Research Interests

  • Morphology Control of Polymers

  • Development of Precise Polycondensation

  • Upcycle Methodology of Polymers

  • Synthesis of High-performance Polymers from Biomass

  • Synthesis of High-performance Polymers

Research Areas

  • Nanotechnology/Materials / Polymer chemistry

Education

  • Osaka University    

    - 1983

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  • Osaka University   工学研究科   プロセス工学

    - 1983

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    Country: Japan

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  • Osaka University   工学部   応用化学

    - 1981

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    Country: Japan

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  • Osaka University    

    - 1981

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Professional Memberships

 

Papers

  • Effect of the blend ratio of cyclic and linear polyethylene blends on isothermal crystallization in the quiescent state

    Keiko Kobayashi, Hironori Atarashi, Shinichi Yamazaki, Kunio Kimura

    Polymer Journal   2023.8

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    Publishing type:Research paper (scientific journal)   Publisher:Springer Science and Business Media LLC  

    Abstract

    The role of entanglements that form between cyclic and linear polymers in crystallization is of particular interest, but it is not fully understood. We investigated the crystallization behaviors of blends of cyclic polyethylene (C-PE) and linear polyethylene (L-PE) in a quiescent state to elucidate the role of this novel entanglement in crystallization. The samples were prepared by mixing the prepared C-PE and L-PE specimens at L-PE weight fraction (ΦL-PE) values of 0–100 wt%, with the weight average molecular weights of C-PE and L-PE being 175 × 103 and 154 × 103, respectively. The isothermal crystallization behaviors were analyzed through polarizing optical microscopy (POM) and differential scanning calorimetry (DSC). The morphology observed through POM was similar to that of ΦL-PE. From the time evolution of the heat flow measured via DSC, we obtained the half-crystallization time (t1/2) values as functions of ΦL-PE at different degrees of supercooling (ΔT). The 1/t1/2 values of the C-PE and L-PE homopolymers were approximately the same at ΔT = 25.5 and 26.5 K. At a larger ΔT value, the 1/t1/2 value of C-PE was significantly larger than that of L-PE. In contrast, 1/t1/2 reached a minimum value at ΦL-PE = 30–40 wt%, irrespective of ΔT. As the entanglement density increased with increasing ΦL-PE, the crystallization rate was expected to decrease monotonically. By considering the experimental relationship between 1/t1/2 and ΦL-PE, we speculated that the suppression of crystallization in the blended system was caused by a novel entanglement formed by the penetration of the L-PE chain into the C-PE chain.

    DOI: 10.1038/s41428-023-00833-1

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    Other Link: https://www.nature.com/articles/s41428-023-00833-1

  • Influence of Preparation Conditions on Porosity of Aromatic Polyamide Hollow Spheres

    Hirofumi Nakayama, Naoto Kibayashi, Hironori Atarashi, Shinichi Yamazaki, Kunio Kimura

    Journal of Fiber Science and Technology   79 ( 8 )   185 - 191   2023

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    Publishing type:Research paper (scientific journal)   Publisher:Society of Fiber Science and Technology Japan  

    DOI: 10.2115/fiberst.2023-0017

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  • Formation of shish-like fibril crystals from the melt of blends of cyclic and linear polyethylene under shear flow

    Keiko Kobayashi, Shinichi Yamazaki, Kunio Kimura

    Polymer Journal   2022.4

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    Publishing type:Research paper (scientific journal)   Publisher:Springer Science and Business Media LLC  

    DOI: 10.1038/s41428-022-00643-x

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    Other Link: https://www.nature.com/articles/s41428-022-00643-x

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

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

    Polymer   202   122660 - 122660   2020.5

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Elsevier BV  

    To clarify the effect of triazole (TR) group at the closing point within the cyclic polymer chain on the crystal growth, we studied morphology and the growth rate of spherulite G of cyclic poly(e-caprolactone) with a TR group at the closing point (C-TR-PCL) as a function of the degree of supercooling Delta T using polarizing optical microscopy. We prepared C-TR-PCLs synthesized by the ring-closing reaction from their linear precursors with M-w = 30000 and 50000, and cyclic PCL polymerized by ring expansion reaction (C-PCL) having no TR group with M-w = 26000, and linear PCL with/without a TR group at a chain end (L-TR-PCL-OH and L-PCL) with M-w = 26000 and 36000, where M-w was determined by GPC using linear polystyrene standards.We found that C-TR-PCL and L-TR-PCL-OH show banded spherulites at small Delta T and band-less normal spherulites with maltese cross at large Delta T. Whereas, C-PCL and L-PCL only showed band-less normal spherulites at any Delta T. This speculates that steric hindrance of TR group near the surface of crystals will become significant at small Delta T. G obeyed the equation, G = G(0)exp(-B/T Delta T), for all the samples. B of C-PCL and L-PCL is constant irrespective of T Delta T, however, that of C-TR-PCL and L-TR-PCL-OH showed two values depending on T Delta T. At the region of lower B, i.e., small Delta T, the banded spherulites could be observed. The change of B corresponds to the morphological change of the spherulites. Since the size of the crystalline region closely related to lamellar thickness becomes large at small Delta T, TR groups excluded from the crystals become to assemble near the surface of the crystals. This is the reason why B becomes low at small Delta T. In C-TR-PCL with higher M-w and L-TR-PCL-OH, the decrease of B with decreasing Delta T becomes small compared to that of C-TR-PCL with lower M-w due to relatively small effect of TR group.

    DOI: 10.1016/j.polymer.2020.122660

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  • A Survey on Consciousness of Kurashiki Canvas and Design Proposals

    Manami Fukumura, Ikuko Turo, Kunio Kimura

    Journal of Fiber Science and Technology   76 ( 4 )   134 - 143   2020.4

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    Authorship:Last author, Corresponding author   Publishing type:Research paper (scientific journal)   Publisher:Society of Fiber Science and Technology Japan  

    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 Reviewed

    Ryogo Ono, Hironori Atarashi, Shinichi Yamazaki, Kunio Kimura

    Polymer   194   122403 - 122403   2020.4

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher:Elsevier BV  

    To elucidate the molecular weight (M-w) dependence of the growth rate of spherulite (G) of cyclic polymers polymerized by the ring expansion reaction, we studied the G of cyclic poly(epsilon-caprolactone) (C-PCL) growing from the melt as a function of the crystallization temperature (T-c) and degree of supercooling (Delta T) using polarizing optical microscopy. We prepared C-PCLs comprising an exclusively repeating unit, excluding other structural units with M-w = 17000, 33000, 41000, 74000 and 85000 and linear PCLs (L-PCL) with M-w = 16000, 35000 and 60000, where M-w was determined by GPC using linear polystyrene standards.G obeyed the equation, G = G(0)exp(-B/T Delta T), for all the samples. The activation energies of secondary nucleation (B) of C-PCL were almost identical except for the C-PCL with the lowest M-w. Since B is proportional to the end surface free energy of the secondary nucleus, it implies that the regularity of the folding surface of C-PCL with high M-w is independent of M-w.Compared to C-PCL and L-PCL having almost the same M-w, G of L-PCL is higher than that of C-PCL at the same T Delta T. This suggests that G of C-PCL and L-PCL is not solely controlled by the entanglement because the entanglement of C-PCL is lower than that of L-PCL. We found the following associations: G(0)alpha M-w(-1.2) for C-PCL and G(0)alpha M-w(-0.67) for L-PCL. The difference in the power of the G(0) dependence on M-w reflects the difficulty of performing sliding diffusion in the secondary nucleus. This strongly supports the hypothesis that the absorption behavior of C-PCL chains in the secondary nucleus on the growth front is significantly different from that of L-PCL.

    DOI: 10.1016/j.polymer.2020.122403

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  • Microspheres with dimple morphology of poly(p-oxyferuloyl) prepared by reaction-induced phase separation

    Hironori Atarashi, Masahaya Sugimoto, Shinichi Yamazaki, Kunio Kimura

    Fiber Society 2018 Spring Conference: Fibers and Textiles for Value Creation in Connected Industries   2018

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    Publishing type:Research paper (international conference proceedings)  

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

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

    POLYMER   111   239 - 243   2017.2

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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 Reviewed

    Daisaku Shojo, Hidekazu Sugimori, Shinichi Yamazaki, Kunio Kimura

    HIGH PERFORMANCE POLYMERS   28 ( 10 )   1139 - 1150   2016.12

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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 Reviewed

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   54 ( 19 )   3094 - 3101   2016.10

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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 Reviewed

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

    POLYMER   98   378 - 386   2016.8

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    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 Reviewed

    Takuya Ohnishi, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF FIBER SCIENCE AND TECHNOLOGY   72 ( 2 )   49 - 53   2016.2

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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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  • High Performance Polyesters Prepared from Bio-Based 2,5-Furandicarboxylic Acid Reviewed

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF FIBER SCIENCE AND TECHNOLOGY   72 ( 2 )   54 - 60   2016.2

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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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  • Preparation of Poly(ether ketone)s Derived from 2,5-Furandicarboxylic Acid by Polymerization in Ionic Liquid Reviewed

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

    MACROMOLECULES   49 ( 4 )   1252 - 1258   2016.2

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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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  • Preparation of poly(ester-imide) ribbons comprised of helical and non-helical blocks by copolymerization Reviewed

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

    RSC ADVANCES   6 ( 104 )   101995 - 102002   2016

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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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  • Synthesis of Poly(ether ketone)s from 2,5-Thiophenedicarboxylic Acid Reviewed

    Yusuke Kanetaka, Shinichi Yamazaki, Kunio Kimura

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

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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 aromatic polyesters by direct polymerization in the presence of boronic anhydride under non-stoichiometric condition Reviewed

    Polymer   66   222 - 229   2015

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

    Daisaku Shojo, Shinichi Yamazaki, Kunio Kimura

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

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    DOI: 10.1002/pola.27791

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

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

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

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    DOI: 10.1002/pola.27683

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  • Crystallization of Polyethylene and Polydioxanone with Multiple Hydrogen Bonds Between Their Terminal Groups Reviewed

    Mika Uchimura, Kohei Okazaki, Shinichi Yamazaki, Kunio Kimura

    KOBUNSHI RONBUNSHU   71 ( 11 )   562 - 572   2014

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    Language:Japanese   Publishing type:Research paper (scientific journal)   Publisher:SOC POLYMER SCIENCE JAPAN  

    In order to clarify the effects of multiple hydrogen bonds between chain ends on the crystal growth of polymers, we studied the growth rate of crystal G of polyethylene (PE) having amino groups and thymine units in the terminal (PE-Thym) and polydioxanone having hydroxy groups and thymine units in the terminal (PDX-Thym) from the melt as a function of the degree of supercooling Delta T by means of polarizing optical microscope, DSC and WAXS. PE-Thym and PDX-Thym have multiple hydrogen bonds between their terminals. We also prepared PE having amino and hydroxy groups in the terminal (PE-OH) and PDX having carboxy and hydroxy groups in the terminal (PDX-OH) as reference samples. Those show weak single hydrogen bond between their terminals. Number average molecular weights M-n of PE-Thym and PE-OH are almost the same (M-n = ca. 2000). M-n of PDX-Thym and PDX-OH are 3000 and 5600, respectively. G of all the samples obeyed the equation, G = G(0) exp(B/Delta T). The exponent B for PE-Thym and PDX-Thym is almost the same as for PE-OH and PDX-OH. Since B is proportional to the surface free energy of the end surface of the nucleus, this indicates that the regularity of folding at the surface is also the same. On the other hand, G(0) of PE-Thym and PDX-Thym is much less than that of PE-OH and PDX-OH. We speculate that the reeling motion from the melt to the nucleus during crystal growth is suppressed due to the formation of a dynamic multiple-hydrogen-bond network between chain ends in the melt. Moreover, in order to shield the multiple hydrogen bonds in the terminal, we studied the Delta T dependence of G for PDX-Thym with added adenine. Compared to PDX-Thym without added adenine, we found that the Delta T dependence of G changed. This indicates that the influence of hydrogen bonds on crystal growth is closely related with the regime of crystal growth.

    DOI: 10.1295/koron.71.562

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

    Yuji Fujitsu, Hirofumi Nakayama, Shinichi Yamazaki, Kunio Kimura

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

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    DOI: 10.1002/pola.26467

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  • Preparation of Novel Naphthalene Polyimide and Its Morphology Reviewed

    Takashi Sawai, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

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

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    DOI: 10.2494/photopolymer.26.341

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

    Toshimitsu Ichimori, Shinichi Yamazaki, Kunio Kimura

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

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    DOI: 10.1002/pola.26839

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

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

    European Polymer Journal   49 ( 8 )   2334 - 2343   2013

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

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

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

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    DOI: 10.1002/app.38554

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

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

    EUROPEAN POLYMER JOURNAL   48 ( 10 )   1787 - 1795   2012.10

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    Language:English   Publishing type:Research paper (scientific journal)   Publisher: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 Reviewed

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

    Polymer (United Kingdom)   53 ( 20 )   4388 - 4398   2012.9

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    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 Reviewed

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

    JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS   50 ( 18 )   1293 - 1303   2012.9

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    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

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

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

    Materials Letters   81   88 - 91   2012.8

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    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 Reviewed

    Uma Thanganathan, Suresh Kumar, Akira Kishimoto, Kunio Kimura

    Materials Letters   72   81 - 87   2012.4

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    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 Reviewed

    Toshimitsu Ichimori, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   49 ( 21 )   4613 - 4617   2011.11

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    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 Reviewed

    Tsunaki Kitahara, Shinichi Yamazaki, Kunio Kimura

    Kobunshi Ronbunshu   68 ( 10 )   694 - 701   2011.10

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    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.

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

    Jin Gong, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    JOURNAL OF APPLIED POLYMER SCIENCE   121 ( 5 )   2851 - 2860   2011.9

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    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 Reviewed

    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   2011.3

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    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

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

    Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    POLYMER   52 ( 3 )   837 - 843   2011.2

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    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 Reviewed

    Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    MACROMOLECULAR CHEMISTRY AND PHYSICS   212 ( 2 )   159 - 167   2011.1

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    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.

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

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

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   49 ( 1 )   127 - 137   2011.1

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    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 Reviewed

    Masahiro Kihara, Shinichi Yamazaki, Kunio Kimura

    POLYMER CHEMISTRY   2 ( 5 )   1195 - 1202   2011

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    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.

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

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

    Polymer Journal   42 ( 5 )   375 - 382   2010.3

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    DOI: 10.1038/pj.2010.20

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

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

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

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    DOI: 10.1002/app.32391

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

    Jin Gong, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

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

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    DOI: 10.1002/macp.201000306

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  • 相分離を伴う重合によって新しい高分子材料を作る(レーダー)

    木村 邦生

    化学と教育   58 ( 6 )   264 - 265   2010

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    DOI: 10.20665/kakyoshi.58.6_264

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

    Shinichi Yamazaki, Manabu Itoh, Takuya Oka, Kunio Kimura

    European Polymer Journal   46 ( 1 )   58 - 68   2009

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  • Proof of a Disentanglement Process of Aliphatic Polyesters via Transesterification by Evaluation of the Growth Rate of Spherulites Reviewed

    YAMAZAKI Shinichi, OKA Takuya, KIMURA Kunio

    66 ( 10 )   475 - 482   2009

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

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

    Macromolecules   42 ( 16 )   6128 - 6135   2009

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    DOI: 10.1021/ma9009033

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

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

    Journal of Adhesion Science and Technology   22 ( 16 )   1985 - 2002   2008.10

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    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.

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  • Composition control of aromatic copolyesters by shearing Reviewed

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

    Macromolecules   41 ( 12 )   4193 - 4199   2008.6

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    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 Reviewed

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

    JOURNAL OF APPLIED POLYMER SCIENCE   108 ( 1 )   85 - 92   2008.4

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    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.

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

    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   2008.3

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    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.

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

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

    Polymer   49 ( 18 )   3928 - 3937   2008

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

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

    Macromolecules   41 ( 4 )   1168 - 1174   2008

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    DOI: 10.1021/ma702030u

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

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

    Macromolecules   41 ( 20 )   7571 - 7578   2008

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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 Reviewed

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

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

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

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

    Polymer   49 ( 7 )   1783 - 1791   2008

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

    Kanji Wakabayashi, Tetsuya Uchida, Shinichi Yamazaki, Kunio Kimura

    Macromolecules   41 ( 13 )   4607 - 4614   2008

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

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

    POLYMER   48 ( 12 )   3429 - 3436   2007.6

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    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 Reviewed

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

    Polymer   48 ( 2 )   458 - 466   2007

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

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

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

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    DOI: 10.1002/pola.22041

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

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

    Macromolecules   40 ( 2 )   239 - 246   2007

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    DOI: 10.1021/ma062032y

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  • 第3回日中繊維シンポジウムに参加して

    木村 邦生

    繊維学会誌   62 ( 12 )   "P - 371"   2006.12

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    DOI: 10.2115/fiber.62.P_371

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

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

    JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY   44 ( 8 )   2732 - 2743   2006.4

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    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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  • Novel Fluorine-containing Poly(aryl ether amide)s derived from 2,3,4,5,6-Pentafluorobenzoic Acid Reviewed

    TANAKA Ken, SATO Natsuko, YAMAZAKI Shinichi, KIMURA Kunio, YAMASHITA Yuhiko

    Sen-ito Kogyo   62 ( 7 )   155 - 161   2006

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    Various amide-containing aryl fluorides were synthesized from 2,3,4,5,6-pentafluorobenzoic acid, and novel fifteen AA-BB type and three AB type fluorine-containing poly(aryl ether amide)s (F-PEA) were obtained by nucleophilic aromatic substitution reaction. The synthesized aryl fluorides possessed several reactive carbons for the nucleophilic attack and cross-linking reaction occurred at 100°C. Polymerizations were carried out at 80°C to avoid cross-linking and stopped just before gelation occurred. They had all para connected linear structures. The obtained F-PEAs showed excellent solubility and afforded tough transparent films by casting method. They also exhibited high Tg in the range of 179-273°C depending on the molecular structure. They showed good thermal stability, and even though F-PEAs contained amide linkage into the repeating unit of polymer molecule, they exhibited excellent hydrophobicity due to the incorporation of 2,3,5,6-tetrafluoro-1,4-phenylene moiety.

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

    Manabu Ohmori, Kunio Kimura, Yuhiko Yamashita, Yoshimitsu Sakaguchi

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

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    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.

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

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

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

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    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.

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

    T Uchida, K Shimantura, K Kimura

    SEN-I GAKKAISHI   59 ( 6 )   207 - 212   2003.6

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    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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  • An attempt to prepare the nonwoven fabric made up of cuprammonium regenerated cellulose fibers by a new method

    YOKOYAMA Fumiyoshi, ONO Takayuki, HARADA Hidetada, KIMURA Kunio, YAMASHITA Yuhiko, MITSUISHI Kazuta, FUJIWARA Kazuko

    Sen-ito Kogyo   56 ( 7 )   371 - 380   2000.7

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    The extrusion of a cuprammonium cellulose solution into the rotational flow field of a disodium dihydrogen ethylenediaminetetraacetate solution led to the formation of the nonwoven fabrics of regenerated cellulose fibers around a rotor. Morphological and structural features of the products were examined by polarized optical microscopy, scanning electron microscopy, and wide-angle X-ray diffraction photography. It was revealed that the constituent fibers have a distinct skin-core strcture. The crystal modification of the fibers was cellulose II. The degree of the chain orientation of the fibers was increased with increasing the draft ratio, with the birefringences of 0.012 to 0.028, which were nearly situated in the same range as those of cuprammonium rayon fibers. The concentrations of the residual copper in the present fabrics were satisfactorily low.

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  • Morphology Control of Rigid Polymers During Polymerization

    Kobunshi   44 ( 4 )   259 - 259   1995.4

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    DOI: 10.1295/kobunshi.44.259

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  • 高分子分子材料の辞典 Reviewed

    木村邦生( Role: Joint author ,  6.基礎編 6-1重縮合)

    高分子学会編 朝倉書店  2022.11 

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    Total pages:591   Responsible for pages:3   Language:Japanese Book type:Dictionary, encyclopedia

  • Polymer Whisker

    1994 

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  • 高分子ウィスカー

    フィラー活用辞典  1994 

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MISC

  • バイオベーススーパーエンジニアリングプラスチック : フランジカルボン酸を原料とした芳香族ポリエーテルケトンの合成

    兼高 悠輔, 山崎 慎一, 木村 邦生

    プラスチックス : 日本プラスチック工業連盟誌   65 ( 7 )   62 - 66   2014.7

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  • マテリアルニュース&トピックス バイオ材料由来の「スーパーエンジニアリングプラスチック」の開発

    兼高 悠輔, 山崎 慎一, 木村 邦生

    Material stage   14 ( 1 )   47 - 51   2014.4

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  • アラミドの中空微粒子の新調製法 Invited

    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

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  • Primary nucleation and crystal growth of cyclic polyethylene under quiescent state

    Shouichi Ida, Tsunaki Kitahara, Shinichi Yamazaki, Kunio Kimura

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   245   2013.4

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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

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  • Eco-preparation of Fiber and Polymer Materials for Sustainable Development of Material-Cycle Society

    KIMURA KUNIO

    Fiber   65 ( 1 )   "P - 20"-"P-22"   2009.1

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  • POLY 37-Composition control of aromatic copolyester by using shear-induced phase separation

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

    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY   235   2008.4

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

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

    Sen-ito Kogyo   64 ( 8 )   216 - 219   2008

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    Microspheres of poly(p-oxycinnamoyl) (POC) were obtained by the polymerization of (E )-4- acetoxycinnamic acid in aromatic solvent at 320degree and a concentration of 1.5% without stirring via liquid-liquid phase separation of oligomers. In contrast to this, rod-like crystals were formed under shearing with more than 700 rpm. The obtained rod-like crystals were 10-15 um in length and 1.0-1.5 um in width having many thorns on the surface. The critical stirring speed for the onset of Taylor vortices was in agreement with 700 rpm and the crystallization of oligomers was hydrodynamically induced by the generation of Taylor vortices affording the rod-like crystals. Stirring influenced the morphology of POC significantly and this work provided a new procedure for the fabrication of fine fibers of intractable aromatic polymers.

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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

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  • Recent progress in morphology control of high performance polymers

    Function & materials   27 ( 12 )   80 - 92   2007.12

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  • Acceleration of Formation of Shish under Flow by Addition of Irregular Shaped Particles

    12 ( 1 )   157 - 160   2007.3

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  • Efficient Chain Extension Reaction of Poly (butylene terephthalate) by using Crystallization

    12 ( 1 )   167 - 171   2007.3

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  • Morphology Control of Polyimides by Using Phase Separation during Polymerization

    KIMURA Kunio

    55 ( 1 )   76 - 78   2006.5

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  • Morphology control of aromatic polymers in concert with polymerization Reviewed

    Kunio Kimura, Shin-ichiro Kohama, Shinichi Yamazaki

    POLYMER JOURNAL   38 ( 10 )   1005 - 1022   2006

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    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.

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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   2005.9

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    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.

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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   2005.6

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    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.

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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   2005.5

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    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   2005.4

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    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.

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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   2005.3

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    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.

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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   2005.3

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    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   2005.3

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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   2005.3

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  • Direct synthesis of poly(4 '-oxy-4-biphenylcarbonyl) and poly(2-oxy-6-naphthoyl) under nonstoichiometric conditions

    S Kohama, K Kimura, T Uchida, S Umehara, Y Ikemoto, Y Yamashita

    POLYMER INTERNATIONAL   54 ( 2 )   471 - 480   2005.2

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    Direct synthesis of poly(4'-oxy-4-biphenylcarbonyl) (POBP) and poly(2-oxy-6-naphthoyl) (PON) was examined by polycondensation of 4'-hydroxy-4-biphenylcarboxylic acid (HBPA) and 2-hydroxy-6-naphthoic acid (HNA) in the presence of 4-ethoxybenzoic anhydride or 2-naphthoic anhydride as condensation reagents. Polymerizations were carried out at 320degreesC in aromatic solvents and liquid paraffin. POBP, having a number-average degree of polymerization (DPn) of 38, was obtained as plate-like crystals at the molar ratio of HBPA and anhydride of 50 mol%. PON was also obtained as plate-like crystals but the DPn was only 13. HBPA and HNA were first converted to reactive acyloxyaromatic acid intermediates. Then the DPn was increased by means of reaction-induced crystallization of oligomers and subsequent solid-state polymerization via an acid-ester exchange under nonstoichiometric conditions caused by the monocarboxylic acid by-product. Even though the DPn of PON was not as high, direct polycondensation of HBPA and HNA proceeded successfully with aromatic anhydrides. (C) 2004 Society of Chemical Industry.

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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   2005.1

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    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   2005.1

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    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).

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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

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    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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  • 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

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    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.

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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

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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   2004.10

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    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.

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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   2004.9

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    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.

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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   2004.6

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    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   2004.2

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    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.

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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   2004.1

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    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.

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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   2003.11

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    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.

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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   2003.11

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    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   2003.10

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    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.

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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   2003.8

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    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   2003.8

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    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.

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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   2003.7

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    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   2003.6

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    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.

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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   2003.6

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    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.

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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   2003.5

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    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.

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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   2003.2

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    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.

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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   2003.2

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    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.

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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

  • 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

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  • Morphology Control of Rigid Polymers by Means of Reaction-induced Phase ,Separation of Oligomers during Solution Polymerization

    KIMURA KUNIO

    Sen-ito Kogyo   59, 285-289 ( 9 )   285 - 289   2003

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    Language:Japanese   Publisher:The Society of Fiber Science and Technology, Japan  

    DOI: 10.2115/fiber.59.P_285

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  • Preparation of aromatic polyesters under unstoichiometric condition by reaction-induced crystallization of oligomers. 1. Polymerization of p-acetoxybenzoic acid in the presence of alkyloxybenzoic acid

    K Kimura, S Kohama, Y Yamashita

    MACROMOLECULES   35 ( 20 )   7545 - 7552   2002.9

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    The polymerization of poly(p-oxybenzoyl) (POB) from p-acetoxybenzoic acid was examined in the presence of three kinds of aromatic monofunctional compounds such as p-hexyloxybenzoic acid (HOBA), p-decyloxybenzoic acid (DOBA) and p-octadecyloxybenzoic acid (OOBA) under unstoichiometric polymerization conditions. Polymerizations were carried out in liquid paraffin at 320 degreesC. POB crystals were obtained by reaction-induced crystallization of oligomers. The obtained POB crystals were found to be consisted of high molecular weight polymers compared with the products obtained by the melt polymerization. Polycondensation proceeded under unstoichiometric condition through following mechanisms; When DPn of oligomers exceeds a critical value, they are crystallized to form the crystals. End-free oligomers are preferentially crystallized due to the lower solubility over end-capped oligomers. End-capped oligomers are also crystallized, and polycondensation proceeds with eliminating end-capping groups of oligomers by trans-esterification just when they are crystallized (mechanism 1). Though a part of the end-capped oligomers are contained in the crystals, end-capping groups are excluded by solid-state polycondensation (mechanism 2). The mechanism 1 is major path in the system of DOBA and OOBA due to the bulkiness of oligomer end groups, and both mechanisms 1, and 2 occur in the system of HOBA.

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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   2002.6

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    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   2002.6

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    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   2002.4

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    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.

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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

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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

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    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

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    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

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    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

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    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

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    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

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    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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  • 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

    木村 邦生, 山下 祐彦

    高分子加工   51, 508-515 ( 11 )   508 - 515   2002

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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   2001.6

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    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   2001.4

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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   2001.4

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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

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    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

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    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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  • 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

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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   2000.8

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    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   2000.8

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    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.

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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   1998.8

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  • 重合過程を利用した生分解性高分子の繊維状単結晶の作製

    木村 邦生

    繊維学会誌   54 ( 3 )   98 - 98   1998.3

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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   1996.4

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    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

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  • Morphology Control of Aromatic Polymers during Polymerization

    1 ( 1 )   221 - 228   1996

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  • Whisker of Rigid-rod Polymers

    Polymeric Material Encyclopedia   8707 - 8713   1996

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  • Poly(benjobisthiajole-imide)s

    Polymeric Material Encyclopedia   5638 - 5641   1996

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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   1995.1

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    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.

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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   1994.3

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    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.

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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   1994.1

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    Language:English   Publishing type:Article, review, commentary, editorial, etc. (scientific journal)   Publisher: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

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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

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    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

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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

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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

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    Language:English   Publisher: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

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  • Morphology Control of Polymer Whiskers

    Polyfile   30 ( 357 )   20 - 22   1993

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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

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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

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

    High Performance Polymers   4 ( 3 )   161 - 171   1992

  • Molecular Weight Change during Poly(p-oxybenzoyl) Whisker Formation

    Yasuo Kato, Yuhiko Yamashita, Kunio Kimura, Seiji Endo, Toshihiko Ohta

    KOBUNSHI RONBUNSHU   47 ( 7 )   583 - 589   1990

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    Language:English  

    Molecular weight changes during poly (p-oxybenzoyl) whisker formation from p-acetoxybenzoic acid in liquid paraffin were studied. Our electron microscope observation suggestd that the needle crystals in the very early stage of polymerization consist of stacks of oligomer lamellae. Here, the degree of polymerization of precipitated oligomers was found to be about 8, from analysis of oligomers dissolved in liquid paraffin by HPLC method. Furthermore, transesterification in the interlamellar regions starts as soon as crystals precipitate. The average DP of whiskers obtained with 3 min after crystal precipitation increases from 8 to 48. These crystals show fibrillation by crushing of whiskers in liquid nitrogen or etching in KOH solution. This fact indicates that reorganization into extended chain crystals occurs accompanied by the increase of DP. On the other hand, DP of the eventual whiskers increased by 1860. That is, the average molecular length exceeds 1 Jim. The formation of such high molecular weight polymers in the solid state polymerization is caused by the closely packed structure of the end groups. © 1990, The Society of Polymer Science, Japan. All rights reserved.

    DOI: 10.1295/koron.47.583

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  • 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

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    Language:Japanese   Publisher: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

  • 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

  • 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

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    Language:Japanese   Publisher:SOC POLYMER SCIENCE JAPAN  

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  • 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

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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

  • 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

  • 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

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    Language:Japanese   Publisher:SOC POLYMER SCIENCE JAPAN  

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  • Poly(p-oxybenzoyl)whiskers (共著)

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

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Presentations

  • 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  2021.11.19 

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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  2021.11.18 

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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  2021.11.18 

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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  2021.11.18 

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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  2021.11.4 

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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  2021.11.4 

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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  2021.9.7 

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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  2021.9.6 

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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  2020.11.6 

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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  2020.11.5 

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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  2020.11.5 

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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  2020.11.5 

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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  2020.6.12 

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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  2020.6.12 

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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  2020.5.27 

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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  2020.5.27 

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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  2020.3.22 

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Works

  • Development of new polymers having irradiation stability

    1999

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  • 耐放射線性高分子材料の開発

    1999

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Awards

  • 繊維学会賞

    2003  

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    Country:Japan

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Research Projects

  • 環状と直鎖状高分子のトポロジカルブレンドの延伸過程の絡み合いと結晶高次構造変化

    Grant number:21K05186  2021.04 - 2024.03

    日本学術振興会  科学研究費助成事業  基盤研究(C)

    山崎 慎一, 木村 邦生, 新 史紀

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    Grant amount:\4290000 ( Direct expense: \3300000 、 Indirect expense:\990000 )

    本研究の目的は、環状と直鎖状高分子の混合によって、絡み合い解消に強弱がつけられるブレンド系に、延伸を加えたときの力学的応答と結晶高次構造の変化を観察することによって、延伸過程の絡み合い変化を伴う構造形成の分子論的メカニズムを理解し、全く新しい結晶性高分子材料の創製に繋げることである。この目的を達成するために、①環状および直鎖状高分子の合成とキャラクタリゼーション②ブレンド高分子の結晶化試料の調製とその延伸過程における応力ひずみ曲線の測定③ブレンド高分子の結晶化試料の延伸過程における結晶高次構造の変化のその場観察を申請者が中心となった研究グループによって行う。
    当該年度は、分子量が193,000の環状と、分子量が93,000または145,000の直鎖状ポリエチレンのブレンド系についての研究を実施した。環状および直鎖状ポリエチレンとして、修飾型Grubbs触媒および第2世代Grubbs触媒によるシクロオクテンの環拡大重合によって調製される前駆体高分子を水素化した環状および直鎖状ポリエチレンを用いた。調製した試料の化学構造の確認を現有のNMRおよび赤外吸収分光計で行った。環状と直鎖状ポリエチレンを所定の割合でブレンドした試料を作製した。
    ブレンド試料の応力ひずみ曲線を室温において引張試験機にて測定した。応力ひずみ曲線の破断ひずみの変化に着目すると、ブレンド成分である直鎖状ポリエチレンの分子量やその組成に応じて、破断ひずみが変化することが明らかになった。

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  • Development of novel chemical recycling system of aromatic polymers by using equilibrium exchange reaction between polymer molecules and cyclic oligomers

    Grant number:18K19877  2018.06 - 2021.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Research (Exploratory)

    Kimura Kunio

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    Grant amount:\4290000 ( Direct expense: \3300000 、 Indirect expense:\990000 )

    In order to establish the sustainable society, chemical recycling system of super-engineering plastics which are comprised of aromatic moieties is important. However, usual chemical recycling of plastics converting to monomers by chemical reaction contained many steps, leading to cost demerit and high energy consumption. From these circumstances, novel chemical recycling system was developed in this study, by using equilibrium exchange reaction between polymer molecules and cyclic oligomers. Bio-base aromatic polymers possessing high-performance were synthesized from biomass and cardo-type compounds extracted from tar. Although aromatic polyesters were difficult to convert cyclic oligomers so far, it was clarified that the aromatic polyamide was better for this system. Now, the optimization of conditions to convert cyclic oligomers and their ring-opening polymerization of aromatic polyamides is examined to establish the novel chemical recycling system.

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  • Crystallization control using entanglement topology that not able to be realized only by linear polymer

    Grant number:17K05998  2017.04 - 2020.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    Yamazaki Shinichi

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    Grant amount:\4810000 ( Direct expense: \3700000 、 Indirect expense:\1110000 )

    In this work, we elucidated the crystallization mechanism of polymers with entanglement topology that cannot be realized by linear polymers alone. It is realized the group of entanglement topology that cannot be realized only by linear polymers by using a mixture of cyclic polymers without knot entanglement and linear or star polymers having complicated knot entanglements.
    Throughout the entire study period, we preformed the studies on blended systems of cyclic and linear or star polyethylene with different molecular weights.
    In-situ observation of the crystallization behavior of the sample under quiescent state and in the flow field was performed by means of polarizing microscopy. We clarified the effect of the entanglement of star-shaped polymer branching points and cyclic and linear chains on the crystallization of the blend system.

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  • Development of flexible transparent conductive materials from the composites of PEDOT:PSS conductive polymer and phenol derivatives as a second dopant

    Grant number:16K06762  2016.04 - 2019.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    Konagaya Shigeji

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    Grant amount:\4810000 ( Direct expense: \3700000 、 Indirect expense:\1110000 )

    Transparent conductive films have been used for the touch panels, of which main material is a semi-conductive inorganic oxide, but it has been required to be replaced by new materials because of the shortage of its flexibility. Since conductive polymer PEDOT:PSS has a shortage of its conductivity, several kinds of additives for itd conductive enhancement have been studied. Phenol derivatives are effective for the conductive enhancement. However it has not been made clear what phenol derivative shows the highest conductive enhancement ability and how it works on the conductive enhancement of PEDOT:PSS. This study disclosed that phenol derivatives with the solubility parameter (SP) values ranging from 14 to 16 have a higher conductive enhancement ability, and that electronic interaction between PEDOT:PSS and a phenol derivative followed by the change of physical properties such as the size and surface charge of PEDOT:PSS nano particles result in the conductive enhancement.

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  • Development of built-up synthesis of high-performance polymer hollow spheres and their usages

    Grant number:16H04205  2016.04 - 2019.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KIMURA KUNIO

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    Grant amount:\15210000 ( Direct expense: \11700000 、 Indirect expense:\3510000 )

    Poly(p-phenylene-5-isophtalamide)(PPHIA) hollow spheres were prepared by the direct polycondensation in aromatic solvent. In order to use these spheres as industrial materials, the methods for size control and porosity control are required. Temperature jump during polymerization and polymerization in poorer solvent were efficient to control the size and it could be changed from 0.7 to 4.3 micrometer by these methods. Further, it was found that the polymerization at 280 degree C at the beginning of the polymerization and then at 320 degree C increased the porosity. Poly(imidazole-amide) did not provide the hollow spheres, even though the microspheres having dimples on the surface were formed.

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  • Development of Optical Resolution Polymerization of Polylactide

    Grant number:15K12245  2015.04 - 2017.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Exploratory Research

    KIMURA Kunio

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    Grant amount:\2600000 ( Direct expense: \2000000 、 Indirect expense:\600000 )

    Poly(L-lactide) (PLLA) is a top runner of biodegradable plastics and the properties iss highly related to the content of unit off D-lactic acid (D-unit) in PLLA. Therefore, the content of D-unit should be strictly controlled. In this study, the new control method of D-unit in PLA was examined by the crystallization during ring-opening cationic polymerization of partial racemic lactide in solution under shearing. The content of D-unit of the precipitated polymer crystals was much lower than the content of D-unit in feed. Further, it was found that the shearing rate influenced on the content of D-unit and higher rate made the content of D-unit lower.

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  • Molecular Weight Control of Cyclic Polyester via Transesterification and its Usability as Nucleating Agents for Linear Analog

    Grant number:15K13788  2015.04 - 2017.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Exploratory Research

    Yamazaki Shinichi, YOSHIDA SAORI

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    Grant amount:\3900000 ( Direct expense: \3000000 、 Indirect expense:\900000 )

    The purpose of this work is to control the molecular weight of cyclic polyesters via shear induced transesterification. It is expected that ring expansion or ring division will be occurred by transesterification of cyclic polyesters. We investigated the applicability of cyclic polyester with controlled molecular weight obtained in this process as a crystallization nucleating agent for homogeneous linear polyester. Detailed examinations are as follows: (1) Synthesis and characterization of cyclic poly(L-lactide) and determination of initial molecular weight, (2) Measurement of molecular weight and distribution of the sample after shear induced transesterification reaction, (3) Availability test of cyclic polyester controlled in molecular weight as a nucleating agent for linear analogues.

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  • Smart Thermal-mechanical Gel Developed by Hierarchical Design

    Grant number:25810123  2013.04 - 2016.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Young Scientists (B)

    Gong Jin, FURUKAWA Hidemitsu, KIMURA Kunio

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    Grant amount:\4290000 ( Direct expense: \3300000 、 Indirect expense:\990000 )

    The aim of this research is to develop smart thermal-mechanical (TM) gel by using special hierarchical structure design method, which is named as Meso-Decoration. In the previous research, the researcher succeeded in controlling simultaneously the primary structure and morphology of high-performance aromatic polymers, and in synthesising the shape memory gel. The TM gel capable of being applied in smart devices is synthesized successfully in this research on the ground of the researcher's hierarchical structure control technology. Furthermore, a prototype of smart button switch unit is made to verify the thermal response function of TM gel.

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  • Development of eco-preparation procedure of aramide from wasted PET

    Grant number:25550070  2013.04 - 2015.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Exploratory Research

    KIMURA Kunio, YAMAZAKI Shinichi, UCHIDA Tetsuya

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    Grant amount:\2860000 ( Direct expense: \2200000 、 Indirect expense:\660000 )

    In order to develop the sustainable society, aramides were prepared by reaction-induced crystallization during ester-amide exchange reaction between PET and aromatic diamines. Further, aromatic polybenzimidazoles were also obtained by the similar procedure between PET and aromatic tetramines. This procedure provides a novel upgrade recycle of PET.

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  • Crystallization control of topological blend polymer which consists of cyclic polymer as a component

    Grant number:24550256  2012.04 - 2015.03

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    YAMAZAKI Shinichi, KIMURA Kunio, UCHIDA Tetsuya, OKIHARA Takumi, KOBAYASHI Keiko

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    Grant amount:\5590000 ( Direct expense: \4300000 、 Indirect expense:\1290000 )

    The purpose of this work is to clarify the role of entanglement species on the crystallization of polymers through observation of crystallization of a topological blend polymer which consists of cyclic polymer. Topological blend polymer means the mixing of cyclic and linear polymers. The following issues were investigated. (1) Several kinds of cyclic and linear polyethylene with different molecular weight were prepared. Crystallization at the quiescent state and under the flow were observed by means of polarizing optical microscope. The degree of supercooling, flow rate and strain dependence of the crystallization behavior were made clear. (2) Observation by a scanning electron microscope and crystal structure analysis by wide angle X-ray diffraction measurement were performed for various blends samples.

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  • Preparation of super-engineering plastics from cellulose

    Grant number:23651084  2011 - 2012

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Challenging Exploratory Research

    KIMURA Kunio, YAMAZAKI Shinichi, UCHIDA Tetsuya

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    Grant amount:\2730000 ( Direct expense: \2100000 、 Indirect expense:\630000 )

    Aromatic polyesters and poly(ether-ketone)s were successfully prepared by the polymerization of 2,5-furanedicarboxylic acid which was derived from biomass. They exhibited excellent thermal stability and chemical resistance comparable with conventional super-engineering plastics derived from the monomers synthesized from petroleum. They possess a great potential to replace the super-engineering plastics.

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  • Built-up synthesis of nanofiber networks of high-performance polymers

    Grant number:21350127  2009 - 2011

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KIMURA Kunio, YAMAZAKI Shinichi, UCHIDA Tetsuya

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    Grant amount:\12740000 ( Direct expense: \9800000 、 Indirect expense:\2940000 )

    Rigid-rod aromatic polymers are expected to possess many excellent properties. However, many of them do not exhibit processability such as solubility and fusibility because of their rigid-rod structure and they had been given up to use as materials. We examined the reaction-induced phase separation during polymerization in order to overcome the antagonistic problem between the high performance and the less processability. The network structures of polyester, polyimides, polybenzimidazoles and poly(ether ketone) were successfully prepared. And further, helical ribbon of poly(ester-imide) and nanofibers of polyazomethine and polyimidazopyrrolone which is a perfect ladder polymer were also obtained.

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  • 回収ポリエチレンを原料とした易リサイクル性・自己修復性樹脂の開発

    Grant number:21651041  2009 - 2010

    日本学術振興会  科学研究費助成事業  挑戦的萌芽研究

    木村 邦生, 山崎 慎一, 内田 哲也

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    Grant amount:\2200000 ( Direct expense: \2200000 )

    ポリエチレン(PE)に代表される汎用プラスチックは石油を原料としており、石油資源の枯渇化ならびに資源循環型社会構築への対応としてリサイクル性の付与が希求されている。しかし、PEはケミカルリサイクル性を有しておらず、PEを原料とて利用することが困難である。本研究では、回収したPEのリサイクル性の向上を目的として、長鎖PEセグメント化ナイロンの調製を検討した。
    PEをキシレン希薄溶液中、85-70℃で結晶化し単結晶を調製した。調製した単結晶を発煙硝酸処理により、結晶の折りたたみ鎖部位を選択的に酸化切断して末端にカルボキシル基を有するテレケリックPE(PEC)を調製した。カルボキシル基/ニトロ基の比率の最も高い条件で酸化処理を行なった。PECを五塩化リンで処理し末端を酸塩化物で封鎖したテレケリックPE(PECC)を調製した。ヘキサメチレンジアミンとPECCを反応させ、PE由来の長鎖ナイロンを調製した。
    PEの単結晶を調製する際の等温結晶化温度を種々変えることで、厚みの異なる4種類の単結晶を調製し、それらを硝酸酸化させることで、炭素数が56、58、65、ならびに70と分子鎖長の異なるテレケリックPEを得た。PEでは吸水がほとんど認められなかったのに対して、長鎖ナイロンでは、いずれも約1~2%の吸水率であり、アミド結合の特徴が現れた。このことより長鎖ナイロンも親水性であること分かった。次に結晶化の条件を揃えて処理したナイロンの結晶性を評価した。全てのサンプルが結晶性を示し、ポリエチレンの斜方晶に特有な二つのピークと同じ面間隔のピークが見られた。示差走査型熱量計測定では、反応前のPECでは融解時にシングルの吸熱ピークが観察されたが、長鎖ナイロンでは複数の吸熱ピークが観察された。これは二重融解挙動であると考えられる。PEセグメントの鎖長の変化に伴う融点の大きな変化は観察されなかった。以上より、結晶化と選択的硝酸酸化を利用することによって、PEとナイロンの特徴を併せ持った材料を調製することができた。

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  • Fractionation and crystallization of wholly aromatic rigid polymer

    Grant number:16550177  2004 - 2005

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    SHIMAMURA Kaoru, UCHIDA Tetsuya, KIMURA Kunio

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    Grant amount:\3200000 ( Direct expense: \3200000 )

    Fractionation of the rigid polymer, poly(p-phenylene benzobisthiazole) (PBZT) was carried out in dilute solution in conc. methane sulfuric acid using silica gels as packing material of a column. Several combinations of the average chain length of the fractionating materials and the average pore diameter of the gels were examined to improve fractionation resolution. The gels with the average pore diameter near to the average chain length resulted in high fractionation resolution. Single crystals of the fractionated and unfractionated PBZT's were observed by TEM. Both single crystals were fundamentally composed of rod crystals with the chain orienting normal to the rods. The unfractionated PBZT made a cluster of parallel rod crystals, where longer chains penetrated a few rod crystals leaving their chain ends within the crystalline core. On the contrary, with the fractionated polymer, extended- chain rod-like crystals were dispersed isolated from each other. This morphology enables us to estimate the chain length visibly by TEM, for which a few milligrams of the material is enough for the observation.

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  • Creation of Environmental-benign polymer composites

    Grant number:13450278  2001 - 2002

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    YAMASHITA Yuhiko, KIMURA Kunio, SHIMAMURA Kaoru

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    Grant amount:\15100000 ( Direct expense: \15100000 )

    Biodegradable polymers do not possess the high mechanical properties, such as strength and elastic modulus, due to the aliphatic chain structure and its orientation and thereby they cannot replace high performance plastics. The composite of biodegradable plastics with reinforcement compensate this problem and hereby the reinforcement possessing not only the high mechanical properties but also good biodegradability is necessary. We have paid attention to prepare the whisker of polyglycolic acid (PGA). The polymers were synthesized in the heterogeneous (liquid-solid) solution polymerization in which an excess of solid glycolide coexists as a buffer to keep the very high glycolide concentration during polymerization in which temperature. As a result PGA whiskers were obtained as mixtures with dendrite crystals.
    The stereoselective synthesis of poly(l-lactic acid) (PLLA) is of great importance because the properties of PLLA are highly related to the stereoregularity. Here, the selective preparation of PLLA from partially rac-lactide is examined by the crystallization during ring-opening polymerization as a novel approach for stereoselective polymerization. Polymerizations of L-lactide and D,L-lactide were carried out at 80℃ in the mixed solvent of toluene and n-octane (40 / 60 by volume). The stereoselective polymerization occurs as follows. Once polymerization is started, homo-oligomer and co-oligomer formed are diastereomeric and thereby the physical properties become different. The homo-oligomers are preferentially precipitated to form the crystals at the early of polymerization due to the lower miscibility into solvent than that of co-oligomer. Thereafter, L-lactide is selectively polymerized at the active chain end of oligomers in the crystals with simultaneous crystallization. D,L-lactide is eliminated from the polymerization site on the crystals by segregation and the PLLA crystals containing less D-lactic acid unit are finally formed from partially rac-lactide

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  • Rigid Polymer Network with Nano pores and its Application for High Performance Materials

    Grant number:13650748  2001 - 2002

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    SHIMAMURA Kaoru, MURAKAMI Syozo, UCHIDA Tetsuya, KIMURA Kunio

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    Grant amount:\4000000 ( Direct expense: \4000000 )

    Rigid polymer networks were prepared by polycondensation of 2, 5-diamino-1, 4-benzene-dithiol with a mixture of terephthalic 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 ε-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 ε-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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  • Development of new methodology for precision polycondensation by means of polymerization-induced oligomer crystallization

    Grant number:12450374  2000 - 2001

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    KIMURA Kunio, SHIMAMURA Kaoru, YAMASHITA Yuhiko

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    Grant amount:\8000000 ( Direct expense: \8000000 )

    In this study, novel methodology for precision polycondensation was examined based on the new concept of the connection between solution oligomerization and solid-state polymerization by reaction-induced crystallization of oligomers.
    Fractional polycondensation: Polymerization of p-acetoxybenzoic acid (p-ABA) and m-acetoxybenzoic acid (m-ABA) were carried out in liquid paraffin (LPF) at 300℃ for 6 hours. Needle-like polymer crystals were obtained by the crystallization of oligomers when the molar ratio of m-ABA in feed was less than 30 mol %. The obtained crystals were comprised of poly(p-oxybenzoyl) and it was concluded that the fractional polycondensation was induced by the difference on the crystallizability between homo- and co-oligomers.
    Sequence control polycondensation: Copolymerizations of p-ABA and S-acetyl-4-mercaptobenzoic acid were carried out in LPF at 300℃. In the case of random copolymerization, spherical polymer products which did not possess any crystal habits were formed in the middle copolymerization ratio due to the lack of crystallizability as well as tendency of liquid-liquid phase separation of oligomers. On the other hand, the copolymerization of dimers or trimers comprised from p-oxybenzoyl and p-mercaptobenzoyl units yield the whiskers at even middle copolymerization ratio. The oligomers prepared from dimers or trimers were precipitated by the crystallization due to the enhancement of sequence regularity and therefore, the copolymer whiskers were formed.
    Polycondensation of unstoichiometric condition: p-ABA was polymerized with p-hexyloxybenzoic acid (HOBA) or p-decyl oxybenzoic acid (DOBA) to break the balance of stoichiometry between acetoxy and carboxylic end groups. The polymer crystals prepared with HOBA of which the molar ratio in feed was 60 % exhibit very high Mn of 4.08×10^3. And those prepared with DOBA of which the molar ratio was 30 % exhibit quite high Mn of 2.78×10^4. It was concluded that Mn increased with eliminating of oligomer end groups terminated by monocarboxylic acids by trans-esterification which occurred simultaneously with crystallization.
    Simultaneous one-pot synthesis of poly(p-oxybenzoyl) and poly(p-aminobenzoyl) Simultaneous one-pot synthesis of poly(p-oxybenzoyl) (POB) and poly(p-aminobenzoyl) (PAB) was examined by means of the reaction induced crystallization of oligomers during solution polymerization. The copolymerizations of p-ABA and p-acetoamidobenzoic acid (AABA) were carried out in triethylbiphenyl mixture at 300℃. Needle-like and plate-like crystals were formed separately at ABA/AABA of 50 〜 30 mol%. Former crystals are mainly comprised of POB and the latter are done of PAB. The miscibility of PAB oligomer to the solvent is much lower than that of POB oligomers due to hydrogen bonding, and hereby the average DPn of phase-separated oligomer of PAB is lower, of which POB oligomer is estimated as 1.90 and PAB oligomer is done as 1.04. Kinetic study reveals that ABA can react four times faster than AABA and this difference leads to the fluctuation of composition in oligomers. Therefore, PAB oligomers tend to be precipitated earlier and PAB crystals are formed at the beginning of the polymerization. Then POB oligomers are precipitated gradually in the middle of polymerization.

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  • 2次の非線形光学材料を目指した剛直高分子単結晶の調製

    Grant number:12875188  2000 - 2001

    日本学術振興会  科学研究費助成事業  萌芽的研究

    山下 祐彦, 木村 邦生, 島村 薫

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    Grant amount:\2400000 ( Direct expense: \2400000 )

    1.緒言:剛直構造からなる芳香族高分子は分子鎖方向に大きな超分極を示すために,2次の非線形光学材料としても注目され始めている。しかし,分子構造が剛直であるゆえに不溶不融であり,材料への成形加工が困難であるという問題を抱えている。そこで本研究では,非線形光学特性が期待できるポリアゾメチンエステル(PAME)の高次構造形成について検討した。
    2.実験:ポリマー換算で1.0wt/vol%になるように4-(4-アセトキシフェニル)イミノ安息香酸(APBA)と重合溶媒を反応容器に入れ,窒素雰囲気中所定温度で6時間重合した。
    3.結果と考察:流動パラフィン(LPF)と芳香族熱媒であるTherm S 1000(TS10,ジベンジルトルエン混合物)を重合溶媒とし,300℃で重合を行った。LPFを用いて重合を行った場合,長さが7im,径が2.5imの紡錘型結晶が35%の収率で得られた。両端が尖っていること,ならびに対称的な形態を示したことより,スパイラル成長によるラメラ晶の積層結晶化により結晶が成長したと推察された。しかしながら,紡錘型結晶の表面がスムーズではなく,ラメラ晶間で,の後重合と再組織化によるラメラ晶積層構造の消失が起きていない。そこで次に,LPFに比べてオリゴマーとの相溶性が高いTS10中で重合を行った。その結果,結晶収率は10%以下と低いが,板状結晶の集合体とともに,長さが40im,径が2imの針状結晶が得られた。LPFに比べてTS10溶媒の方がアスペクト比が高く、長い針状結晶が生成することが分かった。効率的な後重合を起こさせるために,TS10中で温度を320℃,350℃に上げて重合を行った。その結果,350℃では長さ方向に成長した長い針状結晶が生成し,その表面は非常に滑らかであった。重合温度を上げることによって,ラメラ晶間での後重合が効率よく起きたためと考えられる。
    4.結論:APBAをTS10中350℃で重合することにより,PAMEの針状結晶が生成することを明らかにした。

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  • Development of New Technology for Control of Length of Aromatic Polyester Whiskers

    Grant number:08555159  1996 - 1997

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

    YAMASHITA Yuhiko, KIMURA Kunio, YOKOYAMA Fumiyoshi

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    Grant amount:\18300000 ( Direct expense: \18300000 )

    The poly (p-oxybenzoyl) (POB) whiskers are prepared by the polymerization of p-acetoxybenzoic acid in liquid paraffin at 330゚C.The polymer chains are aligned to the long axis of the whisker and it shows the single crystal nature. Therefore, this whisker has a high potential for applications of structural materials, devices and so on. In this project, we aim to develop the control method of the POB whisker length.
    It is revealed that the formation mechanism of the whiskers includes the following steps ; 1) oligomers are precipitated by crystallization to form the lamellae, 2) the lamellae pile up along the long axis of the needle-like crystals with a spiral growth caused by screw dislocation, 3) DP increases by post-polymerization in the interlamellar regions. In this mechanism, the tip angle of the whiskers is constant at 80゚ up to 20min, whereas it becomes significantly sharper to 7-8゚ at 30 min. The growth rate of the step at the small radius of curvature decrease due to the increase of the strain energy of secondary nucleation, and therefore the spiral appears to rotate with uniform angular velocity under a steady state within 20 min. It is necessary to depress the sharpening and lengthen the period of the steady growth increase the length. In order to compensate the decreased concentration of oligomers, oligomers are added into the polymerization system after 15 min.just before when the tips angle becomes sharper. The addition of oligomers lengthens the steady growth period from 20 min.to 30 min., and then the length increases 16%. The length increases continuously by the second addition and the whiskers having the 32% increased length are obtained. The result show the new method for the control of the whisker length.

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  • 組成変調を有する高分子単結晶の傾斜材料作製に関する基礎的研究

    Grant number:08650798  1996

    日本学術振興会  科学研究費助成事業  基盤研究(C)

    木村 邦生, 横山 文義

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    Grant amount:\2500000 ( Direct expense: \2500000 )

    溶液重合過程でのポリ(4-オキシベンゾイル)(POB)のウィスカ-生成に与える共重合成分の化学構造、ならびに共重合様式の影響を検討した。
    (1)4-アセトキシ安息香酸(ABA)とS-アセトキシ-4-メルカプト安息香酸との流動パラフィン(LPF)中での溶液共重合について検討した。ランダム共重合の場合は、ABAの仕込み比が60〜90モル%ではオリゴマーの液-液相分離により球状微粒子が生成してしまい、70モル%以上、ならびに10モル%以下の場合にのみウィスカ-は生成する。また、生成物の共重合組成は仕込み組成とほぼ一致しており、重合結晶化過程での成分分別は起こらない。これは、両モノマーの反応性に差がないこと、ならびにオリゴマーの相分離挙動が組成に依存しないことに起因していると推察される。ポリ(4-オキシベンゾイル-co-4-メルカプトベンゾイル)を与える交互共重合の場合は、ウィスカ-が生成した。
    (2)ABAと3-クロロ-4-アセトキシ安息香酸とのLPF中での共重合では、ランダム共重合の場合は、ABAの仕込み比が80モル%以上の場合にのみウィスカ-が生成した。交互共重合の場合は微粒子のみが生成し、ウィスカ-は生成しない。しかし、ポリ(4-オキシベンゾイル-per-4-オキシベンゾイル-per-3-クロロ-4-オキシベンゾイル)を与える周期性共重合を行うとウィスカ-を生成する。
    (3)ABAと3-メトキシ-4-アセトキシ安息香酸のLPF中での溶液共重合では、ランダム共重合の場合はABAの仕込み比が90モル%以上の場合しかウィスカ-は生成せず、交互ならびに(2)と同様な周期性共重合の場合もウィスカ-の生成は見られない。
    以上より、共重合成分が結晶性を低下させる程度に応じて共重合の規則性を高めることにより、共重合ウィスカ-の調製が可能であることが分かった。

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  • 精密重縮合技術の開発

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  • 高性能高分子の高次構造制御

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  • 新規高性能高分子の合成

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  • New methodology for precision polycondensation

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  • Morphology control of high performance polymers

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  • Synthesis of Novel high performance polymers

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  • Seminar in Environmental Polymer Chemistry (2021academic year) Late  - その他

  • Seminar in Environmental Polymer Chemistry (2021academic year) Late  - その他

  • Seminar in Environmental Polymer Chemistry (2021academic year) Prophase  - その他

  • Precise Polymerization Methodology (2021academic year) Prophase  - その他

  • Polymer Chemistry Ⅱ (2021academic year) Third semester  - 木3~4

  • Polymer Chemistry I (2021academic year) 1st semester  - 火3~4

  • Polymer Chemistry Ⅰ (2021academic year) 1-3 semesters  - [第1学期]火3~4, [第2学期]その他, [第3学期]木3~4

  • Polymer Chemistry Ⅰ (2021academic year) 1-3 semesters  - [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 (2020academic year) Summer concentration  - その他

  • Introduction to Environmental Chemistry (2020academic year) 1st semester  - 木1,木2

  • Organic Chemistry Ⅳ (2020academic year) 1st semester  - 金4,金5

  • Organic Chemistry Ⅴ (2020academic year) Second semester  - 火2,火3

  • Organic Chemistry Ⅲ (2020academic year) 1st and 2nd semester  - [第1学期]金4,金5, [第2学期]火2,火3

  • Special Research (2020academic year) Year-round  - その他

  • Modern Chemistry (2020academic year) Third semester  - 金1,金2,金3

  • Modern Chemistry (2020academic year) Third semester  - 金1,金2,金3

  • Modern Chemistry (2020academic year) Third semester  - 金1,金2,金3

  • Introduction to Modern Chemistry (2020academic year) 3rd and 4th semester  - 火9

  • Introduction to Environmental Chemistry (2020academic year) 1st semester  - 木1,木2

  • Environmental Polymer Synthesis (2020academic year) Late  - 月2,月3

  • Seminar in Environmental Polymer Chemistry (2020academic year) Prophase  - その他

  • Seminar in Environmental Polymer Chemistry (2020academic year) Late  - その他

  • Seminar in Environmental Polymer Chemistry (2020academic year) Late  - その他

  • Seminar in Environmental Polymer Chemistry (2020academic year) Prophase  - その他

  • Precise Polymerization Methodology (2020academic year) Prophase  - その他

  • Polymer Chemistry Ⅱ (2020academic year) Third semester  - 木2,木3

  • Polymer Chemistry I (2020academic year) 1st semester  - 火2,火3

  • Polymer Chemistry Ⅰ (2020academic year) 1-3 semesters  - [第1学期]火2,火3, [第2学期]その他, [第3学期]木2,木3

  • Polymer Chemistry Ⅰ (2020academic year) 1st semester  - 火2,火3

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