研究者情報

マスター

アカウント（マスター）

• 氏名

  中野　環(ナカノ　タマキ), ナカノ　タマキ

所属（マスター）

• 触媒科学研究所　高分子機能科学研究部門

所属（マスター）

• 触媒科学研究所　高分子機能科学研究部門

独自項目

syllabus

• 2021, 分子化学（高分子機能科学）, Molecular Chemistry (Macromolecular Science), 修士課程, 総合化学院, 高分子，立体化学，立体特異性，コンホメーション，光学活性，キラリティー，らせん構造
• 2021, 環境と人間, Environment and People, 学士課程, 全学教育, 触媒、化学物質、環境とエネルギー、持続的な社会発展
• 2021, 一般教育演習(ﾌﾚｯｼｭﾏﾝｾﾐﾅｰ), Freshman Seminar, 学士課程, 全学教育, ?分?、?分?合成、?性能?分?、機能性?分?、?分性?分?、プラスチック、繊維、ゲル、
• 2021, 触媒化学, Catalytic Chemistry, 学士課程, 理学部, 触媒，触媒化学，表面科学，高分子化学，理論化学

PositionHistory

• 触媒科学研究所附属触媒連携研究センター長, 2018年4月1日, 2020年3月31日
• 触媒科学研究所附属触媒連携研究センター長, 2020年4月1日, 2022年3月31日
• 触媒科学研究所附属触媒連携研究センター長, 2022年4月1日, 2024年3月31日

researchmap

プロフィール情報

学位

• 工学博士（大阪大学）

プロフィール情報

• 姓

  中野, ナカノ

• 名

  環, タマキ

• ID各種

  200901017246956799

対象リソース

http://polymer.cat.hokuda.ac.jp/index.html

業績リスト

研究キーワード

• 円偏光   精密重合   π-電子系ポリマー   キラルポリマー   controlled polymerization   pi-electronic polymers   chiral polymers   

研究分野

• ナノテク・材料 / 高分子化学

経歴

• 1999年 - 2006年 奈良先端科学技術大学院大学 物質創成科学研究科 助教授 助教授
• 1999年 - 2006年 Associate Professor
• 2006年 - 北海道大学大学院工学研究科 教授 教授
• 2006年 - Professor
• 1998年 - 1999年 名古屋大学大学院工学研究科 助教授 助教授
• 1998年 - 1999年 Associate Professor
• 1990年 - 1998年 名古屋大学工学部応用化学科 助手 （岡本佳男教授） 助手
• 1990年 - 1998年 Research Associate,1990 Assistant Professor, Nagoya University1998 Associate Professor, Nagoya University1999 Associate Professor, Nara Institute of Science and Technology2006 Professor, Hokkaido University

学歴

•         - 1991年   大阪大学
•         - 1990年   大阪大学   基礎工学研究科   化学専攻 博士課程 中退
•         - 1990年   大阪大学
•         - 1988年   大阪大学   基礎工学研究科   化学専攻 修士課程
•         - 1988年   大阪大学
•         - 1986年   大阪大学   基礎工部合成化学科
•         - 1986年   大阪大学

委員歴

• 2016年 - 現在   日本化学会   命名法委員会
• 2004年 - 現在   高分子学会   高分子命名法委員会

受賞

• 2009年 高分子学会賞
  
• 1996年 高分子学会ポリマージャーナル論文賞
  
• 1996年 1996 SPSJ Award for the Outstanding Paper in Polymer Journal
  

論文

• Recyclable and efficient polyurethane-Ir catalysts for direct borylation of aromatic compounds

  Akihiro Kimura, Haruka Hayama, Jun-ya Hasegawa, Hassan Nageh, Yue Wang, Naofumi Naga, Mayumi Nishida, Tamaki Nakano

  POLYMER CHEMISTRY 8 47 7406 - 7415 2017年12月 [査読有り][通常論文]
   

  Four polyurethanes comprising 2,2'-bipyridyl moieties incorporated in the main chain were synthesized as a novel polymer ligand for the Ir(I)-catalyzed direct borylation of aromatic compounds. The polyurethanes were insoluble in common organic solvents and soluble in dimethylsulfoxide. The borylation reaction of benzene catalyzed by Ir(I) in the presence of the polymer prepared from 4,4'-bis(hydroxylmethyl)-2,2'-bipyridyl and 1,6-diisocyanatohexane led to the catalytic activities comparable to that in the presence of 2,2'-bipyridyl, while the polymers prepared by the reactions of 4,4'-bis(hydroxylmethyl)-2,2'-bipyridyl with 1,4-diisocyanatobenzene, 1,4-diisocyanato-3-methylbenzene, and bis(4-isocyanatophenyl)methane possesed lower catalytic activities. The high activity observed using the 1,6-diisocyanatohexane-based polyurethane catalyst could have a connection to the fact that this polymer has the highest tendency to form the inter-chain hydrogen bond. The borylation reaction systems with the polymers were biphasic, where the top and bottom layers contained the product and the polymer-based catalysts, respectively. Due to the phase separation, the product isolation and catalyst recycle were readily performed through a simple decantation. The catalyst prepared from 1,6-diisocyanatohexane-based polyurethane was able to be recycled at least five times without a significant decrease in activity. Further, the regio-selectivity in borylation of toluene, anisole, and trifluoromethybenzene was studied using the polyurethane ligands as well as the corresponding small-molecular ligands.
• Photo-induced β-elimination of 9-fluorenylmethanol leading to dibenzofulvene.

  Nageh H, Zhao L, Nakayama A, Hasegawa JY, Wang Y, Nakano T

  Chemical communications (Cambridge, England) 53 60 8431 - 8434 2017年08月 [査読有り][通常論文]
   

  An effective photo-induced beta-elimination of an alcohol leading to a vinyl compound is introduced for the first time. 9-Fluorenylmethanol was irradiated in a solution using a Xe lamp and was efficiently converted to dibenzofulvene (DBF) (9-methylenefluorene) in the absence of base which is necessary in the corresponding ground-state reaction.
• pi-Stacked poly(vinyl ketone)s with accumulated push-pull triphenylamine moieties in the side chain

  Heng Wang, Yue Wang, Xichong Ye, Haruka Hayama, Hiroyoshi Sugino, Hideyuki Nakano, Tamaki Nakano

  POLYMER CHEMISTRY 8 4 708 - 714 2017年01月 [査読有り][通常論文]
   

  A novel triphenylamine containing vinyl ketone monomer, isopropenyl 4-[bis(4-methylphenyl) amino] phenyl ketone (IMAPK), was prepared from bis[(4-methylphenyl) amino] benzene and methacryloyl chloride through the Friedel-Crafts acylation. t-Butyl 4-[bis(4-methylphenyl) amino] phenyl ketone (BMAPK) was also synthesized as a monomeric unit model. IMAPK was homopolymerized and copolymerized with styrene under free-radical conditions. While homopolymerizability of IMAPK was rather low, copolymers with styrene were obtained at fair monomer conversions. The obtained polymers were proposed to possess a rather rigid, restricted conformation in which the side-chain chromophores are p-stacked on the basis of NMR spectra, and they indicated remarkable hypochromicity and red shifts in absorbance spectra and red shifts in emission spectra compared with BMAPK. In addition, the polymers exhibited red shifts in the emission spectra of which the extent was higher in a more polar solvent among cyclohexane, tetrahydrofuran, chloroform, and acetonitrile; this observation was ascribed to the conformational relaxation of the side-chain 4-[bis(4-methylphenyl) amino] phenyl group in excited states which is facilitated in a polar solvent. The conformational relaxation may be facilitated also by close interactions between the side-chain chromophore groups along the polymer chain. In addition, polymer aggregation was found to occur in solution where the size of aggregates was greater in cyclohexane than in tetrahydrofuran. Further, the polymers showed reduced oxidation potentials compared with BMAPK in cyclic voltammetry analysis, supporting that they have a pi-stacked conformation.
• Isolation and phototransformation of enantiomerically pure iridium(III) bis[(4,6-difluorophenyl)pyridinato-N,C-2]picolinate

  Yue Wang, Takunori Harada, Yoshihito Shiota, Kazunari Yoshizawa, Heng Wang, Sheng Wang, Xichong Ye, Masamichi Ogasawara, Tamaki Nakano

  RSC ADVANCES 7 47 29550 - 29553 2017年 [査読有り][通常論文]
   

  Here we report the resolution of phosphorescent light-emitting iridium(III) bis[(4,6-difluorophenyl) pyridinato-N, C-2]-picolinate into its respective enantiomers by using chiral HPLC and the photo-induced transformation of the isolated enantiomers.
• Photo Racemization and Polymerization of (R)-1,1 '-Bi(2-naphthol)

  Zhaoming Zhang, Yue Wang, Tamaki Nakano

  MOLECULES 21 11 2016年11月 [査読有り][通常論文]
   

  (R)-1,1'-Bi(2-naphthol) ((R)-BINOL) in an acetonitrile solution lost optical activity upon irradiation with an Hg-Xe lamp. HPLC resolution of the product indicated that (R)-BINOL was racemized upon irradiation, and SEC analysis suggested that a polymeric product was formed in the course of racemization. It is proposed that polymerization of BINOL can occur before it is racemized and that a unit in a polymer derived from BINOL may lose its optical activity afterwards due to in-chain racemization and/or reduction. The polymeric products seem to consist not only of BINOL residues but also of residues derived from acetonitrile as well as those derived through reduction of BINOL.
• Synthesis and Properties of Modified Amylose Containing an Aryl Spacer at a Regular Interval in Its Main Chain

  Yasuhito Koyama, Tamaki Nakano

  CHEMISTRY LETTERS 45 8 1018 - 1020 2016年08月 [査読有り][通常論文]
   

  We describe the synthesis and properties of modified amylose containing an aryl spacer at a regular interval in its main chain as a new host polymer. The modified amylose was efficiently synthesized by copper-catalyzed alkyne-azide 1,3-dipolar cycloaddition polymerization of alkyne-containing permethylated maltohexaosyl azide 3. The polymer exhibited greater hydrophobicity than permethylated amylose. A mixture of the polymer with terthiophene formed an inclusion complex in a 10% dimethyl sulfoxide aqueous solution, leading to intermolecular chirality transfer from the polymer to terthiophene.
• Chirality induction using circularly polarized light into a branched oligofluorene derivative in the presence of an achiral aid molecule

  Yue Wang, Alexander L. Kanibolotsky, Peter J. Skabara, Tamaki Nakano

  CHEMICAL COMMUNICATIONS 52 9 1919 - 1922 2016年 [査読有り][通常論文]
   

  Chirality induction into a uniform, star-shaped fluorene oligomer with a central truxene moiety (T3) was achieved using circularly polarized light in the presence of achiral fluorene or phenanthrene. Induction into T3 alone was difficult, suggesting that close chain packing realized through interactions of T3 with small molecules plays a role in chirality induction.
• Synthesis of poly(1,10-phenanthroline-5,6-diyl)s having a π-stacked, helical conformation.

  Yang W, Nakano T

  Chemical communications (Cambridge, England) 51 97 17269 - 17272 2015年12月 [査読有り][通常論文]
   

  5,6-Dibromo-1,10-phenanthroline and 2,9-di-n-butyl-5,6-dibromo-1,10-phenanthroline were polymerized using a Ni catalyst to afford helical polymers in which the phenanthroline moieties are densely stacked on top of each other. Polymerization of the latter monomer using a chiral catalyst led to a preferred-handed helix. This is the first Ni-catalyzed helix-sense-selective polymerization of aromatic compounds.
• Chiral Polyurethane Synthesis Leading to pi-Stacked 2/1-Helical Polymer and Cyclic Compounds

  Prashant G. Gudeangadi, Takeshi Sakamoto, Yukatsu Shichibu, Katsuaki Konishi, Tamaki Nakano

  ACS MACRO LETTERS 4 9 901 - 906 2015年09月 [査読有り][通常論文]
   

  (R)-1,1'-Bi(2-naphthol) was reacted with 1,4-phenylene diisocyanate leading to a mixture of linear polyurethane and cyclic compounds including a cyclic dimer and a cyclic trimer. The structure of the cyclic dimer was elucidated by X-ray crystal structure analysis. The polymer was proposed to possess a rather stiff, pi-stacked, 2/1-helical conformation on the basis of NMR, CD, and UV spectra and molecular dynamics simulations. The conformation was stable in the range of temperature of 0-60 degrees C.
• Polymer Education in Japan

  Tamaki Nakano

  MACROMOLECULAR SYMPOSIA 355 1 61 - 67 2015年09月 [査読有り][招待有り]
   

  Education in Japan is segmented into 6 years of elementary school, 3 years of junior high school, 3 years of high school, and 4 years of university, with elementary and junior high education compulsory. Polymer education in Japan starts at the elementary school level, where the iodine-starch reaction is taught, typically as hands-on, experimental lessons in a science class. At the high school level, the concepts of "polymers" and "polymerization" are taught in chemistry class but not in detail. Details are treated as optional subjects in the curriculum and are not included in university entrance exams; students generally do not choose to spend much time and efforts on subjects that are not applicable to the exams. Polymer science is taught as an independent subject or an area of organic chemistry or material science at the university level.
• Chiral Polyurethane Synthesis Leading to π‑Stacked 2/1-Helical Polymer and Cyclic Compounds

  中野 環

  ACS MacroLett 4 9 901 - 906 2015年09月 [査読有り][通常論文]
   

  (R)-1,1'-Bi(2-naphthol) was reacted with 1,4-phenylene diisocyanate leading to a mixture of linear polyurethane and cyclic compounds including a cyclic dimer and a cyclic trimer. The structure of the cyclic dimer was elucidated by X-ray crystal structure analysis. The polymer was proposed to possess a rather stiff, pi-stacked, 2/1-helical conformation on the basis of NMR, CD, and UV spectra and molecular dynamics simulations. The conformation was stable in the range of temperature of 0-60 degrees C.
• Predicting the Switchable Screw Sense in Fluorene-Based Polymers

  Adriana Pietropaolo, Yue Wang, Tamaki Nakano

  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 54 9 2688 - 2692 2015年02月 [査読有り][通常論文]
   

  A chirality-switching free-energy landscape was reconstructed on a 43-mer of poly(9,9-dioctylfluoren-2,7-diyl) (PDOF). The simulations were conducted on amorphous silica surface as well as in the vacuum phase for a single chain or for a group of sixteen chains. The achiral-to-chiral transition occurs only on amorphous silica (activation free-energy 35kcalmol(-1)), where the enantiomeric (homochiral) basins are detected. This was supported by the experiments where effective chirality induction to PDOF using circularly polarized light (CPL) was attained only for a film deposited on a quartz glass and not for a solution or a suspension. These results indicate that interactions of PDOF with amorphous silica play a crucial role in chirality switching. Importance of chain assembling was also indicated. Theoretical ECD spectra of the enantiomeric basins containing a 5(1) helix reproduce the experimental spectra.
• Ring-opening polymerization of a 2,3-disubstituted oxirane leading to a polyether having a carbonyl-aromatic pi-stacked structure

  Maia Merlani, Yasuhito Koyama, Hiroyasu Sato, Li Geng, Vakhtang Barbakadze, Bezhan Chankvetadze, Tamaki Nakano

  POLYMER CHEMISTRY 6 11 1932 - 1936 2015年 [査読有り][通常論文]
   

  2-Methoxycarbonyl-3-(3,4-dimethoxyphenyl) oxirane was synthesized and polymerized using a cationic initiator to afford a polymer having a rather stiff, stretched conformation. The side-chain methoxycarbonyl group and 3,4-dimethoxyphenyl group of neighboring monomeric units may form a hetero pi-stacked structure between side-chain carbonyl and aromatic groups which leads to intramolecular charge transfer (ICT) interactions. 2-Ethoxy-carbonyl- 3-phenyloxirane failed in polymerization, leading only to small molecules including cyclic compounds.
• Ring-opening polymerization of a 2,3-disubstituted oxirane leading to a polyether having a carbonyl-aromatic pi-stacked structure (vol 6, pg 1932, 2015)

  Maia Merlani, Yasuhito Koyama, Hiroyasu Sato, Geng Li, Vakhtang Barbakadze, Bezhan Chankvetadze, Tamaki Nakano

  POLYMER CHEMISTRY 6 12 2356 - 2356 2015年 [査読有り][通常論文]
  
• A high triplet-energy polymer: synthesis and photo-physical properties of a pi-stacked vinyl polymer having a xanthone moiety in the side chain

  Hiroyoshi Sugino, Yasuhito Koyama, Tamaki Nakano

  RSC ADVANCES 5 27 21310 - 21315 2015年 [査読有り][通常論文]
   

  Poly(xanthon-3-ylmethacrylate) (poly(XOMA))and poly(xanthon-3-yl methacrylate-co-methyl methacrylate) (poly(XOMA-co-MMA)) having a pi-stacked conformation were synthesized as host material candidates for phosphorescence-based light emitting diodes. Poly(XOMA) harvested photo excitation energy for blue phosphorescent emission of iridium bis[(4,6-difluorophenyl) pyridinato-N, C-2] picolinate (FIrpic) in a CHCl3 solution and in film.
• 光のキラリティーを用いた高分子らせんの構築

  中野 環

  化学工業 66 2 92 - 96 2015年 [査読有り][招待有り]
  
• Ring-opening Polymerization of a 2,3-Disubstituted Oxirane Leading to a Polyether Having a Carbonyl-Aromatic -Stacked Structure

  中野 環

  Polymer Chemistry 6 11 1932 - 1936 2015年 [査読有り][通常論文]
   

  2-Methoxycarbonyl-3-(3,4-dimethoxyphenyl) oxirane was synthesized and polymerized using a cationic initiator to afford a polymer having a rather stiff, stretched conformation. The side-chain methoxycarbonyl group and 3,4-dimethoxyphenyl group of neighboring monomeric units may form a hetero pi-stacked structure between side-chain carbonyl and aromatic groups which leads to intramolecular charge transfer (ICT) interactions. 2-Ethoxy-carbonyl- 3-phenyloxirane failed in polymerization, leading only to small molecules including cyclic compounds.
• Right-handed 2/1 helical arrangement of benzene molecules in cholic acid crystal established by experimental and theoretical circular dichroism spectroscopy

  Heng Wang, Adriana Pietropaolo, Wenbin Wang, Chen-Yi Chou, Ichiro Hisaki, Norimitsu Tohnai, Mikiji Miyata, Tamaki Nakano

  RSC ADVANCES 5 122 101110 - 101114 2015年 [査読有り][通常論文]
   

  The right-handed two-fold helical (2/1 helical) arrangement of benzene included in the cavity of cholic acid (CA) crystal was directly established by experimental and theoretical circular dichroism (CD) spectral studies. Experimental spectra comprised chirality elements of benzene and CA and well agreed with the theoretical spectra which considered interactions between benzene and polar groups of CA.
• Tricks of Light on Helices: Transformation of Helical Polymers by Photoirradiation

  Tamaki Nakano

  CHEMICAL RECORD 14 3 369 - 385 2014年06月 [査読有り][招待有り]
   

  The following polymer structural transitions were achieved using light: preferred-handed helix formation for poly(9,9-di-n-octylfluoren-2,7-diyl), helix racemization (helix-helix transition) for poly(2,7-bis(4-t-butylphenyl)fluoren-9-yl acrylate) and poly(2,5-bis[4-((S)-2-methylbutyloxy)phenyl]styrene), and helix decomposition for poly(2,7-bis(4-t-butylphenyl)-9-methylfluoren-9-yl acrylate) and poly(2,7-bis(4-t-butylphenyl)fluoren-9-ylmethyl methacrylate). Although these types of transitions and chemical transformations have been studied mainly using heat or chemicals as stimuli, light can also cause these structural alterations. In the helix construction and the helix-helix transition, a key transition is a twist-coplanar conformational change of a biphenyl or an aryl-aryl unit in the side chain or the main chain of the polymer. Furthermore, the helix-helix transition was caused only by light and not by heat. The examples discussed in this review are expected to trigger off a new direction in synthesis and reaction of chiral polymers.
• Photo-induced helix-helix transition of a polystyrene derivative

  Yue Wang, Takeshi Sakamoto, Yasuhito Koyama, Yuma Takanashi, Jiro Kumaki, Jiaxi Cui, Xinhua Wan, Tamaki Nakano

  POLYMER CHEMISTRY 5 3 718 - 721 2014年02月 [査読有り][通常論文]
   

  Poly(2,5-bis[4-((S)-2-methylbutyloxy)phenyl]styrene) having a helical conformation underwent helix-helix transition upon photo-irradiation. Conformational transition can significantly alter polymer properties, and so far thermal stereomutation has been studied. However, as for photo-induced mutation, only helix-helix transition (irreversible CD-active to CD-silent helix transition) of a polyacrylate has been explored. Here, we present mutation of the polystyrene derivative. Chiroptical, viscometric, and vibrational spectroscopic analyses indicated the polymer mutated from an optically active helix to another optically inactive helix with a different shape.
• Gigantic chiroptical enhancements in polyfluorene copolymers bearing bulky neomenthyl groups: importance of alternating sequences of chiral and achiral fluorene units

  Kento Watanabe, Yasuhito Koyama, Nozomu Suzuki, Michiya Fujiki, Tamaki Nakano

  POLYMER CHEMISTRY 5 3 712 - 717 2014年02月 [査読有り][通常論文]
   

  An alternating copolymer consisting of achiral and chiral units emits remarkably efficient CPL on photo-excitation. The main-chain twist bias is enhanced by thermal annealing by the factor of 10(4) in the ground state. An anisotropy factor of the polymer in the excited state is greater by approximately an order of magnitude compared with that in the ground sate.
• Studies on Photodecomposition of an Oxime Sulfonate

  Toshikage Asakura, Hitoshi Yamato, Keita Tanaka, Ryuichi Takahashi, Hisatoshi Kura

  JOURNAL OF PHOTOPOLYMER SCIENCE AND TECHNOLOGY 27 2 227 - 230 2014年 [査読有り][通常論文]
  
• Molecular mechanism of polyacrylate helix sense switching across its free energy landscape

  Adriana Pietropaolo, Tamaki Nakano

  Journal of the American Chemical Society 135 15 5509 - 5512 2013年04月17日 [査読有り][通常論文]
   

  Helical polymers with switchable screw sense are versatile frameworks for chiral functional materials. In this work, we reconstructed the free energy landscape of helical poly(2,7-bis(4-tert-butylphenyl)fluoren-9-yl acrylate) [poly(BBPFA)], as its racemization is selectively driven by light without any rearrangement of chemical bonds. The chirality inversion was enforced by atomistic free energy simulations using chirality indices as reaction coordinates. The free energy landscape reproduced the experimental electronic circular dichroism spectra. We propose that the chirality inversion of poly(BBPFA) proceeds from a left-handed 31 helix via multistate free energy pathways to reach the right-handed 31 helix. The inversion is triggered by the rotation of biphenyl units with an activation barrier of 38 kcal/mol. To the best of our knowledge, this is the first report on the chiral inversion mechanism of a helical polymer determined in a quantitative way in the framework of atomistic free energy simulations. © 2013 American Chemical Society.
• Molecular chirality induction to an achiral π-conjugated polymer by circularly polarized light

  Wang, Yue, Sakamoto, Takeshi, Nakano, Tamaki

  Chemical Communications 48 13 1871 - 1873 2012年 [査読有り][通常論文]
   

  A preferred-handed helical conformation was induced to poly(9,9-dioctylfluoren-2,7-diyl) (PDOF) in a thin film form upon irradiation with single-handed circularly polarized light (CPL) where the induction was reversible.
• Organic semiconductor compounds with high charge mobility and organic thin films comprising them

  Nakano, Tamaki, Sakamoto, Takeshi, Tanaka, Kenta, Higashimura, Hideyuki

  2012年 [査読有り][通常論文]
  
• Organic semiconductor compound

  Nakano, Tamaki, Sakamoto, Takeshi, Tanaka, Kenta, Higashimura, Hideyuki

  2012年 [査読有り][通常論文]
  
• Compound and film containing same for electroluminescent display devices

  Higashimura, Hideyuki, Kobayashi, Norifumi, Nakano, Tamaki, Sakamoto, Takeshi, Yu, Jin-Meng

  2012年 [査読有り][通常論文]
  
• Method for modifying polymer compound and method for producing films containing modified polymer compounds

  Higashimura, Hideyuki, Kobayashi, Norifumi, Nakano, Tamaki, Sakamoto, Takeshi

  2012年 [査読有り][通常論文]
  
• Light creates polymer helicity

  Nakano, Tamaki

  Kobunshi 61 10 767 - 768 2012年 [査読有り][通常論文]
  
• A study on conformational regulation of polymer chains by photostimulation

  Nakano, Tamaki

  Asahi Garasu Zaidan Josei Kenkyu Seika Hokoku a 1 - 6 旭硝子財団 2012年 [査読無し][通常論文]
  
• A Photo-Degradable Helix: Synthesis, Structure, and Photolysis of Optically Active Poly[2,7-bis(4-t-butylphenyl)-9-methylfluoren-9-yl Acrylate]

  Takeshi Sakamoto, Kento Watanabe, Yukatsu Shichibu, Katsuaki Konishi, Shin-Ichiro Sato, Tamaki Nakano

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 49 4 945 - 956 2011年02月 [査読有り][通常論文]
   

  2,7-Bis(4-t-butylphenyl)-9-methylfluoren-9-yl acrylate (BBPMFA) was synthesized and polymerized using alpha,alpha'-azobisisobutyronitrile or n-Bu(3)B-air as a radical initiator and using the complex of 9-fluorenyllithium with (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine as an optically active anionic initiator. Although the radical polymerization led to rather low-molecular-weight products at low yields, the anionic polymerization afforded polymers with higher molecular weights in higher yields. The poly(BBPMFA) obtained by the anionic polymerization was slightly rich in isotacticity (meso diad 57%) and showed an intense circular dichroism (CD) spectrum and large dextrorotation. The intensity of the CD spectrum and magnitude of optical activity increased with an increase in M(n), suggesting that the polymer possesses a preferred-handed helical conformation. The CD spectrum disappeared within 1 s on irradiation to the polymer in a CHCl(3) solution using a 500-W Hg-Xe lamp. This was ascribed to fast photolysis of the ester linkage leading to a loss of helical conformation of the entire chain. Photolysis products of poly(BBPMFA) were poly(acrylic acid) and 2,7-bis(4-t-butylphenyl)-9-methylenefluorene (2,7-bis(4-t-butylphenyl)dibenzofulvene). The photolysis reaction seemed to proceed through the "unzipping" mechanism. The rate constant of photolysis of poly(BBPMFA) under irradiation at monochromated 325 nm was around 0.01 s(-1) independent of molecular weight. Photolysis at 325 nm was approximately 2400 times faster than that for chemical ester solvolysis under a neutral condition in the dark. (C) 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 49: 945-956, 2011
• Asymmetric Anionic Polymerization of 2,7-Bis(4-t-butylphenyl)fluoren-9-ylmethyl Methacrylate and Photoinduced Structural Transition of the Obtained Polymer

  Kento Watanabe, Takeshi Sakamoto, Tamaki Nakano

  CHIRALITY 23 1E E28 - E34 2011年 [査読有り][通常論文]
   

  2,7-Bis(4-t-butylphenyl) fluoren-9-ylmethyl methacrylate (BBPFMMA) was synthesized as a new candidate of a bulky monomer suitable for asymmetric anionic polymerization (IUPAC nomenclature: asymmetric helix-chirogenic polymerization) leading to a preferred-handed helical, optically active polymer. The new monomer was polymerized using the complex of 9-fluorenyllithium and (S)-(1)-1-(2-pyrrolidinylmethyl) pyrrolidine in toluene at -78 degrees C. As opposed to the original intention to obtain a polymethacrylate, the monomer seemed to undergo structural transition (decomposition) giving 2,7-bis(4-t-butylphenyl) dibenzofulvene and the obtained polymer was most probably a terpolymer of BBPFMMA, 2,7-bis(4-t-butylphenyl) dibenzofulvene, and methacrylic acid. The obtained polymer showed circular dichroism (CD) spectra, indicating that chirality had been introduced to the copolymer chain during the course of polymerization. On photo irradiation, the polymer underwent a structural transition involving a remarkable decrease in apparent molecular weight measured by size-exclusion chromatography (SEC) and changes in FT-IR spectral patterns. However, the CD spectrum of the polymer was not obviously altered by irradiation, indicating that polymer chirality is not affected by light. Chirality 23: E28-E34, 2011. (C) 2011 Wiley Periodicals, Inc.
• Chiral hyperbranched polymer emitting efficient circularly polarized light (CPL)

  Nakano, Tamaki, Watanabe, Kento, Sakamoto, Takeshi

  Fain Kemikaru 40 9 40 - 46 シーエムシー出版 2011年 [査読有り][通常論文]
  
• A chiral π-stacked vinyl polymer emitting white circularly polarized light

  Watanabe, Kento, Sakamoto, Takeshi, Taguchi, Makoto, Fujiki, Michiya, Nakano, Tamaki

  Chemical Communications 47 39 10996 - 10998 2011年 [査読有り][通常論文]
   

  An optically active, pi-stacked poly[2,7-bis(4-tert-butylphenyl)dibenzofulvene] having a preferred-handed helical conformation was synthesized by anionic polymerization. A thin film sample of the polymer exhibited broad-band white circularly polarized light (CPL) emission on photo excitation.
• Synthesis and efficient circularly polarized light emission of an optically active hyperbranched poly(fluorenevinylene) derivative

  Juin-Meng Yu, Takeshi Sakamoto, Kento Watanabe, Seiichi Furumi, Nobuyuki Tamaoki, Yun Chen, Tamaki Nakano

  CHEMICAL COMMUNICATIONS 47 13 3799 - 3801 2011年 [査読有り][通常論文]
   

  An optically active, hyperbranched poly(fluorenevinylene) derivative was synthesized by polymerization of (-)-2,4,7-tris(bromomethyl)-9-neomenthyl-9-pentylfluorene. A spin-coated film sample of the polymer exhibited efficient circularly polarized light (CPL) emission in the visible range of 400-700 nm on photo excitation even without annealing processes leading to chain ordering.
• A Reactive Helix: Synthesis, Chemical Modification, and Polymerization of an Optically Active Polymethacrylate

  Takeshi Sakamoto, Toshio Nishikawa, Yasuyuki Fukuda, Shin-ichiro Sato, Tamaki Nakano

  MACROMOLECULES 43 14 5956 - 5963 2010年07月 [査読有り][通常論文]
   

  1-(p-Vinylphenyl)dibenzosuberyl methacrylate (VDBSMA) having two reactive vinyl groups in a molecule was synthesized and polymerized using alpha,alpha'-azobis(isobutyronitrile) as a radical initiator and using the complexes of 9-fluorenyllithium with (S)-(+)-1-(2-pyriolidinylmethyl)pyrrolidine, (-)-sparteine, and (S,5)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane as optically active anionic initiators The lice radical polymerization led to an insoluble material, indicating that both methacrylic and styrenic moieties participated in the polymerization and a doss-linked gel was produced In contrast, the anionic polymerization proceeded exclusively through the addition reaction of methacrylic moiety leaving the styrenic vinyl group intact leading to soluble polymers The resulting poly(VDBSMA)s having a polymethacrylate-type main-chain structure were highly isotactic and showed high optical activity and intense circular dichroism (CD) spectra, indicating that the polymers have a single-handed helical conformation Thus, a single-handed helical polymer having side-chain vinyl groups, which can be chemically modified, was successfully synthesized The side-chain vinyl group was converted to 2-hydroxyethyl group, 1,2-dihydroxyethyl group, and carboxylic acid group by polymer reaction without seriously deterriorating the single-handed helical conformation of the polymer. In this way, single-handed helical polymers with side-chain protonic groups which would be difficult to be prepared by direct asymmetric anionic polymerization of the corresponding monomers were conveniently synthesized In addition, radical polymerization of poly(VDBSMA) as a macromonomer afforded an optically active adduct consisting of single-handed helical chains
• Synthesis, structure and function of π-stacked polymers

  Nakano, Tamaki

  Polymer Journal 42 2 103 - 123 2010年02月 [査読有り][通常論文]
   

  Macromolecular conformation often has a significant effect on the properties of polymeric materials, and hence, conformational control in synthesizing a polymer is an important goal in polymer science. As a new conformational motif of vinyl polymers having side-chain pi-electronic groups, we have introduced a 'pi-stacked structure' in which side-chain chromophores are regularly stacked on top of each other and main-chain C-C bonds have a nearly all-trans, zigzag conformation. pi-Stacked polymers can be prepared by vinyl polymerization of dibenzofulvene (DBF) and its derivatives. On the basis of the controlled structure, poly(DBF) and its derivatives exhibit unique photophysical and electronic properties as vinyl polymers. In addition, introduction of chirality to pi-stacked polymers was also achieved. In this review, the synthesis of poly(DBF) and its derivatives and their structural analyses and properties are described. Polymer Journal (2010) 42, 103-123; doi:10.1038/pj.2009.332
• Synthesis and photo-induced stereomutation of a single-handed, optically active helical polyacrylate

  Nakano, Tamaki, Sakamoto, Takeshi, Sato, Shin-ichiro

  Abstracts of Papers, 239th ACS National Meeting, San Francisco, CA, United States, March 21-25 2010年 [査読有り][通常論文]
  
• Synthesis, polymer chain conformational structure, and photoelectronic properties of π-stacked polymers

  Nakano, Tamaki

  Kobunshi 59 3 164 - 168 2010年 [査読有り][通常論文]
  
• Optical device used as optical switche and optical modulator

  Nakano, Tamaki, Sakamoto, Takeshi, Higashimura, Hideyuki

  2010年 [査読有り][通常論文]
  
• Synthesis and photo-induced stereomutation of a single-handed helical, optically active polyacrylate

  Nakano, Tamaki, Sakamoto, Takeshi, Sato, Shin-ichiro

  Polymer Preprints 51 1 145 - 146 2010年 [査読有り][通常論文]
  
• Synthesis and opto-electronic function of π-stack polymers

  nakano tamaki

  Mirai Zairyo 10 10 25 - 31 2010年 [査読有り][通常論文]
  
• A Reactive Helix: Synthesis, Chemical Modification, and Polymerization

  Macromolecules 5956  2010年 [査読無し][通常論文]
  
• Synthesis and structure of an optically active π-stacked poly(dibenzofulvene) bearing chiral terminal group

  Nakano, Tamaki, Tanikawa, Mitsuru, Nakagawa, Osamu, Yade, Tohru, Sakamoto, Takeshi

  Journal of Polymer Science, Part A: Polymer Chemistry 47 1 239 - 246 2009年01月 [査読有り][通常論文]
   

  Dibenzofulvene (DBF) affords a polymer having pi-stacked conformation by anionic, cationic, and free-radical polymerization. In this study, DBF was polymerized anionically using potassium menthoxide as initiator to obtain optically active poly(DBF) having a chiral menthoxy group as a terminal group. The obtained polymer indicated circular dichroism (CD) absorption bands in the absorption wavelength range of fluorenyl group, indicating that chiral conformation was induced to the stacked main chain by the influence of the terminal group. The CD intensity was reversibly affected by temperature of measurement; hence, the chiral conformation may be rather dynamic. The effect of the terminal group was found to decrease as the chain length increased. Theoretical CD calculation indicated that the obtained polymer has a left-banded helical conformation and that the dihedral angle between neighboring monomeric units might be about 10-20 degrees. (c) 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 239-246, 2009
• Photoinduced Racemization of an Optically Active Helical Polymer Formed by the Asymmetric Polymerization 2,7-Bis(4-tert-butylphenyl)fluoren-9-yl Acrylate

  Takeshi Sakamoto, Yasuyuki Fukuda, Shin-ichiro Sato, Tamaki Nakano

  ANGEWANDTE CHEMIE-INTERNATIONAL EDITION 48 49 9308 - 9311 2009年 [査読有り][通常論文]
  
• Charge delocalization over stacked π-electron systems

  Nakano, Tamaki, Yade, Tohru

  Chemistry Letters 37 3 258 - 259 2008年03月 [査読有り][通常論文]
   

  Cation radicals of oligomers and polymers of dibenzofulvene having a pi-stacked conformation showed broad absorption bands based on charge resonance in near IR region, which red-shifted with increasing degree of polymerization, indicating that charge delocalization takes place through multiple, stacked fluorene moieties.
• Chiral macromolecules and their stationary phases for chromatography and chromatography packings for optical isomer separation

  Nakano, Tamaki, Yaegashi, Takayuki, Tsuji, Masashi

  2008年 [査読有り][通常論文]
  
• Optically active luminescent polymers and their manufacture

  Nakano, Tamaki, Higashimura, Hideyuki

  2008年 [査読有り][通常論文]
  
• Dibenzofulvene-type monomers and polymers, their compositions with high electric conductivity, and charge transporters using them

  Nakano, Tamaki, Kotani, Akihiro, Gao, Mingtien

  2008年 [査読有り][通常論文]
  
• Nanoparticle formation by irreversible in situ aggregation of rigid π-stacked segments of a flexible-rigid block copolymer

  Nakano, Tamaki, Yade, Tohru, Fukuda, Yasuyuki, Takewaki, Kazuyuki

  Chemistry Letters 36 2 320 - 321 2007年02月 [査読有り][通常論文]
   

  Block copolymers of dibenzofulvene and methyl methacrylate obtained by living anionic polymerization formed stable, soluble nanoparticles by in situ molecular aggregation of the poly(dibenzofulvene) segments having a rigid pi-stacked conformation; the nanoparticles indicated red-shifted absorption bands and reduced oxidation potential relative to a single chain poly (dibenzofulvene).
• Composition with asymmetric structure and simple process for producing the same

  Nakano, Tamaki, Yaegashi, Takayuki, Tuji, Masashi

  2007年 [査読有り][通常論文]
  
• Synthesis, structure, and function of π-stacked polymers

  Nakano, Tamaki

  Jasco Report 49 1 1 - 6 ジャスコレポート社 2007年 [査読有り][通常論文]
  
• Charge-transporting materials containing fluorene polymers

  Nakano, Tamaki, Kotani, Akihiro, Gao, Ming-Tien

  2007年 [査読有り][通常論文]
  
• Probing Charge Transport in π-Stacked Fluorene-Based Systems

  Coropceanu, Veaceslav, Nakano, Tamaki, Gruhn, Nadine E, Kwon, Ohyun, Yade, Tohru, Katsukawa, Ken-Ichi, Bredas, Jean-Luc

  Journal of Physical Chemistry B 110 19 9482 - 9487 2006年05月 [査読有り][通常論文]
   

  The molecular parameters governing charge transport along a pi-stacked fluorene chain in poly( dibenzofulvene) are studied by a joint experimental and theoretical approach involving high-resolution gas-phase photoelectron spectroscopy and quantum-mechanical methods. We specifically investigate the electronic couplings between fluorene moieties as well as the intramolecular reorganization energies, for both holes and electrons. Our results indicate that a pi-stacked fluorene chain favors hole transport over electron transport. The values for electronic couplings and reorganization energies estimated here are compared with those derived recently for pentacene.
• Anionic polymerization of 2,7-Di-t-butyldibenzofulvene: Synthesis, structure, and photophysical properties of the oligomers with a π-stacked conformation

  Yade, Tohru, Nakano, Tamaki

  Journal of Polymer Science, Part A: Polymer Chemistry 44 1 561 - 572 2006年01月 [査読有り][通常論文]
   

  2,7-Di-t-butyldibenzofulvene (tBu(2)DBF), a bulky dibenzofulvene derivative, was polymerized using n-butyllithium as initiator in tetrahydrofuran at -78 degrees C and in toluene at 0 degrees C. tBu(2)DBF afforded mainly oligomers up to trimer even at [monomer](0)/[initiator](0) = 20 ([monomer](0) = 0.2 M) at -78 degrees C and 0 degrees C, indicating that this monomer is much less reactive than dibenzofulvene (DBF), its parent compound. The reaction at the same [monomer](0)/[initiator](0) ratio at an elevated [monomerlo gave a small amount of insoluble polymer. The oligomers indicated a hypochromic effect in the absorption spectra and only monomer emission in the fluorescent spectra. The conformation of the trimer and the dimer was examined by means of NOESY NMR spectra and semiempirical calculations. In the trimer conformation, the fluorene moieties of the central and the initiation-side monomeric units were found to be closely stacked on top of each other, while the termination-side monomeric unit appeared to be in a faster conformational dynamics compared with the other monomeric units. Although the dimer seemed to have a relatively flexible conformation, a pi-stacked structure appeared to be involved in the conformational dynamics to show hypochromicity. The results of this study suggest that the reported intramolecular excited dimer (excimer) formation of the poly- and oligo(DBF)s [J Am Chem Soc 2003, 125, 15474] is based on a slight, local conformational change upon photo absorption, leading to a closer pi-stacked alignment of two neighboring fluorene units than that in the ground state. Such a local conformational transition may be difficult for the tBu(2)DBF trimer because of steric repulsion of the t-butyl groups. (c) 2005 Wiley Periodicals, Inc.
• Asymmetric polymerization of 2,7-dipentyldibenzofulvene

  Tamaki Nakano, Takayuki Yaegashi, Osamu Nakagawa, Masashi Tsuji, Mitsuru Tanikawa

  KOBUNSHI RONBUNSHU 63 7 492 - 497 2006年 [査読有り][通常論文]
   

  2,7-Dipentyldibenzofulvene (PDBF) was synthesized and anionically polymerized using complexes of 9-fluorenyllithium and optically active ligands. The obtained poly (PDBF) s having no asymmetric centers showed intense circular dichroism in film due purely to the chiral conformation of the main chain.
• Optically active copolymer as chromatography packings for optical-isomer separation and its preparation

  Nakano, Tamaki, Yaegashi, Takayuki, Tuji, Masashi

  2006年 [査読有り][通常論文]
  
• Free-radical polymerization of dibenzofulvene leading to a π-stacked polymer: Structure and properties of the polymer and proposed reaction mechanism

  Nakano, Tamaki, Yade, Tohru, Fukuda, Yasuyuki, Yamaguchi, Takashi, Okumura, Shohei

  Macromolecules 38 20 8140 - 8148 2005年10月 [査読有り][通常論文]
   

  Free-radical polymerization of dibenzofulvene (DBF) was carried out under various conditions. The radical polymerization proceeded exclusively in vinyl fashion without isomerization of the growing radical or aromatic substitution by the initiator fragment. The polymerization was highly conformation-specific (stereospecific), giving a polymer with a pi-stacked conformation in which the main-chain C-C bonds are nearly all trans and the side-chain fluorene moieties are stacked on top of each other. The conformation specificity (stereospecificity) of the DBF radical polymerization was almost similar to that in the anionic polymerization although the radical polymerization products appeared to have a small amount of irregular, defective conformation incorporated into the mostly pi-stacked chain. The conformation specificity was affected by the initial monomer concentration and reaction temperature. This observation was explained by a proposed mechanism where two types of the growing radicals having different conformations mediate the polymerization. The poly(DBF) obtained by the radical polymerization showed lower fluorescent intensity and higher solubility possibly due to a small amount of conformational defects.
• Synthesis of fluorenyl potassium species with potassium t-butoxide (t-BuOK) and its use for anionic polymerization

  T Nakano, O Nakagawa, M Tanaka, T Yade, M Tsuji

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 43 5 1150 - 1154 2005年03月 [査読有り][通常論文]
  
• Synthesis and function of a π-stacked polymer

  Nakano, Tamaki

  Kagaku Kogyo 56 3 195 - 202 2005年 [査読有り][通常論文]
  
• Radical polymerization using molecular templates

  Nakano, Tamaki

  Kagaku 60 8 66 - 67 2005年 [査読有り][通常論文]
  
• Stereospecific polymerization of 9-fluorenyl methacrylate: Tacticity effects on the thermal and photophysical properties of the polymers

  H Ishizawa, T Nakano, T Yade, M Tsuji, O Nakagawa, T Yamaguchi

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 42 18 4656 - 4665 2004年09月 [査読有り][通常論文]
   

  Poly(9-fluoreneyl methacrylate) was obtained through anionic polymerization with t-BuLi and t-BuMgBr and through radical polymerization with alpha,alpha'-azobisisobutyronitrile. Anionic polymerization with t-BuLi in tetrahydrofuran and radical polymerization afforded syndiotactic polymers (rr similar to 90%), whereas anionic polymerization with Li and Mg initiators in toluene and CH,Cl, led to isotactic polymers. The thermal and photophysical properties of the polymers were examined. A syndiotactic polymer tended to show higher glass transition and decomposition temperatures than an isotactic polymer. However, polymers with different tacticities were not likely to assume specific, distinctive conformations such as a helix or a pi-stacked conformation in solution. An isotactic polymer showed stronger interactions in a CH,Cl, solution with 2,4,7-trinitro-9-fluorenylidenemalononitrile, an electron-acceptor molecule, than a syndiotactic polymer. (C) 2004 Wiley Periodicals, Inc.
• Synthesis of polymer gel with chiral helical cavity by molecular imprinting using bifunctional vinyl monomers

  S Habaue, T Satonaka, T Nakano, Y Okamoto

  POLYMER 45 15 5095 - 5100 2004年07月 [査読有り][通常論文]
   

  The molecular imprinting method was applied for synthesizing gels with a chiral helical cavity using various bifunctional vinyl monomers, such as alpha-(benzyloxymethyl)acrylic acid derivatives as a monomer, and one-handed helical (+)-poly(diphenyl-2-pyridylmethyl methacrylate) as a template. The chiral gels were almost quantitatively prepared after removal of the template polymer by hydrolysis of the ester groups. The obtained gels exhibited chiral resolution powers toward various racemates, such as trans-stilbene oxide and Troger's base, and the substituents on the phenyl group of the monomer significantly affected the recognition ability. The observed separation factors were higher than those of the gels prepared from the mono-functional vinyl monomer, methacrylic acid. (C) 2004 Published by Elsevier Ltd.
• Viscoelastic behaviors and molecular motions of highly syndiotactic poly(vinyl alcohol) fibers

  Y Gotoh, Y Nagara, T Nakano, Y Okamoto, Y Ohkoshi, M Nagura

  JOURNAL OF POLYMER SCIENCE PART B-POLYMER PHYSICS 42 5 800 - 808 2004年03月 [査読有り][通常論文]
   

  The viscoelastic behavior and molecular motion of highly syndiotactic poly(vinyl alcohol) (S-PVA) fibers with a dyad syndiotacticity (r) of 69% were studied by dynamic mechanical thermal analysis and wide-angle X-ray diffraction and compared with those of atactic poly(vinyl alcohol) (A-PVA) fibers with r = 54%. The beta(c) dispersion, based on the molecular motion of the chain molecules in the crystalline regions, was observed for A-PVA around 120-140 degreesC, and the only primary (alpha(c)) dispersion was observed for S-PVA around 180 degreesC. The thermal expansion coefficients for the a and c axes of the A-PVA crystal changed discontinuously around 120 degreesC, which corresponded to the beta(c) dispersion. For S-PVA, the coefficient for the (002) plane changed discontinuously around 100 degreesC, similarly to A-PVA, but that for the (100) plane remained unchanged between 20 and 220 degreesC. These results showed that the intermolecular hydrogen bonding of S-PVA was stronger in the direction of the a axis than in the other directions, suppressing the beta(c) dispersion. The storage modulus and thermal expansion coefficient of the (020) plane (molecular axis) of S-PVA decreased markedly around 180 degreesC, and this indicated that the alpha(c) dispersion was due to the torsional motion of the molecular chains in the crystalline regions. (C) 2004 Wiley Periodicals, Inc.
• Charge transport in a π-stacked poly(dibenzofulvene) film

  Nakano, Tamaki, Yade, Tohru, Yokoyama, Masaaki, Nagayama, Norio

  Chemistry Letters 33 3 296 - 297 2004年03月 [査読有り][通常論文]
   

  Hole drift mobility of poly(dibenzofulvene) was found to be 2.7 x 10(-4) cm(2)V(-1) s(-1) at 299 K at a field strength of 7 x 10(5) Vcm(-1) by the time-of-flight (TOF) measurement on a cast film containing 2,4,7-trinitrofluorenylidene-9-malononitrile as an electron acceptor. This value is higher than that of main-chain pi-conjugating poly(pi-phenylenevinylene) (I X 10(-5) cm(2)V(-1)s(-1)), is comparable to that of main-chain sigma-conjugating poly(methylphenylsilane) (I x 10(-4) cm(2)V(-1)s(-1)), and is slightly lower than that of Se (10(-4) cm(2)V(-1)s(-1) order), an inorganic semiconductor.
• Crystalline block copolymers and adhesives using them for semiconductor wafer dicing

  Nakano, Tamaki, Ando, Takashi

  2004年 [査読有り][通常論文]
  
• Poly(2,7-di-n-pentyldibenzofulvene) showing chiroptical properties in the solid state based purely on a chiral conformation

  T Nakano, O Nakagawa, M Tsuji, M Tanikawa, T Yade, Y Okamoto

  CHEMICAL COMMUNICATIONS 2 144 - 145 2004年01月 [査読有り][通常論文]
   

  Poly(2,7-di-n-pentyldibenzofulvene)s with no stereocenters, obtained by anionic polymerization using chiral 9-fluorenyllithium ligand complexes, showed intense circular dichroism in film form due purely to the chiral conformation of the main chain, while no chiroptical properties were detectable in solution.
• Method for production of molecule-recognition polymers useful as stationary phase for chromatography

  Okamoto, Yoshio, Habagami, Shigeki, Nakano, Tamaki

  2004年 [査読有り][通常論文]
  
• π-Stacked poly(dibenzofulvene): Structure and photophysical/electronic properties

  Nakano, Tamaki, Yade, Tohru

  Abstracts of Papers, 227th ACS National Meeting, Anaheim, CA, United States 2004年 [査読有り][通常論文]
  
• π-Stacked poly(dibenzofulvene): structure and photophysical/electronic properties

  Nakano, Tamaki, Yade, Tohru

  Nakano, Tamaki; Yade, Tohru 45 1 191  2004年 [査読有り][通常論文]
  
• Asymmetric polymerization of N-cyclohexylmaleimide using an O-2-optically active Co(II) complex

  T Nakano, T Yade

  KOBUNSHI RONBUNSHU 61 4 282 - 288 2004年 [査読有り][通常論文]
   

  Asymmetric radical polymerization of N-cyclohexylmaleimide was attempted using alpha,alpha'-azobisisobutyronitrile (AIBN) as an initiator and (R,R)-N,N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminatocobalt(II) (1) as an optically active additive in a tetrahydrofuran-pyridine mixture and in pure tetrahydrofuran: the reaction was only inhibited by the cobalt complex. However, it was found that introduction of a small amount Of O-2 or air to the inhibited reaction system in tetrahydrofuran-pyridine effectively promoted polymerization, and AIBN was not necessary to achieve the polymerization. O-2 or air did not promote polymerization in pure tetrahydrofuran. A reaction mechanism involving an anionic propagating species was proposed; interaction Of 1-O-2 complex with the monomer caused electron transfer from the former to the latter, generating an anionic species in which coordination of pyridine to Co seems to be indispensable. The polymers obtained in the 1-O-2-monomer systems were optically active, based on a chiral main-chain configuration.
• Production method of living polymerization catalysts

  Nakano, Tamaki

  2004年 [査読有り][通常論文]
  
• Development of new anion polymerization initiator, aiming ease use for precise polymerization method

  Nakano, Tamaki, Yaudem, Tohru, Nakagawa, Osamu, Tsuhi, Masashi

  Setchaku 48 8 352 - 359 2004年 [査読有り][通常論文]
  
• Synthesis, structure, and photophysical and electrochemical properties of a π-stacked polymer

  Nakano, Tamaki, Yade, Tohru

  Journal of the American Chemical Society 125 50 15474 - 15484 2003年12月 [査読有り][通常論文]
   

  Dibenzofulvene (DBF) was polymerized using anionic initiators to afford a vinyl polymer. Oligo(DBF)s having from two to eight side-chain fluorene moieties bearing different chain-terminal groups were isolated by preparative size-exclusion chromatography. The structures of the isolated oligomers were revealed by single-crystal X-ray and H-1 NMR analyses. Both in solution and in crystal, the in-chain fluorene moieties stacked on top of each other, while the terminal conformation varied depending on the terminal group. These conformational characteristics were supported by molecular mechanics and dynamics calculations. The oligomers and polymers indicated hypochromism and red shift in UV absorption spectra and exclusive excimer emission in fluorescence spectra. In addition, reduced oxidation potentials were observed for the oligomers in electrochemical analyses, which suggests charge delocalization over the a-stacked electron systems. The photophysical and electrochemical effects increased with the chain length of the oligomers and leveled off around the chain length of an oligomer consisting of five fluorene units.
• Revised interpretation for N-cyclohexylmaleimide polymerization in the presence of an optically active cobalt(II) complex: Polymerization mediated by anionic species formed through monomer-Co(II) complex-O-2 interaction

  T Nakano, T Yade, Y Okamoto

  MACROMOLECULES 36 10 3498 - 3504 2003年05月 [査読有り][通常論文]
   

  This report revises the interpretations of the reaction mechanism in the polymerization of N-cyclohexylmaleimide (CHMI) in the presence of alpha, alpha'-azobis(isobutyronitrile) (AIBN) and (R, R)-N, N'-bis(3,5-di-tert-butylsalicylidene)-1,2-cyclohexanediaminatocobalt(II) (1) [Macromolecules 2000,33, 1489]. Although we proposed that the reaction was mediated by a radical species and that the interaction between growing polymer radical with 1 induced chirality in the main chain in the earlier report, the results in the present article indicate that the systems reported in the earlier report were most probably contaminated by a small amount of air and that the polymerization proceeds via an anionic species that was produced by the interaction of the monomer, 1, and O-2. The effect of the contamination was overlooked due to the lack of a control experiment using O-2 in the absence of AIBN in our earlier study. In this work, the polymerization of CHMI was performed in the presence and absence of 1, O-2, alpha, alpha'-azobis-(isobutyronitrile) (AIBN), and protonic additives (methanol and acetic acid). The results indicated the following: (1) the polymerization in a tetrahydrofuran-pyridine mixture occurs in the presence of 1 and a small amount of oxygen even without using AIBN; (2) the reaction does not take place in the presence of 1 alone or in the presence of 1 and AIBN under a strictly controlled N-2 atmosphere; (3) a small amount of AcOH completely inhibits the polymerization with 1 and O-2 while 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) does not kill the reaction; and (4) the polymer was likely to possess -OH or -OOH groups at the chain terminals (a telechelic structure). On the basis of these observations, we withdraw our earlier, wrong interpretation that the polymerization is mediated by a radical species and conclude that the polymerization and the observed stereochemistry are effected by an anionic mechanism.
• Solid-state polymerization of dibenzofulvene leading to a copolymer with oxygen

  T Nakano, O Nakagawa, T Yade, Y Okamoto

  MACROMOLECULES 36 5 1433 - 1435 2003年03月 [査読有り][通常論文]
  
• Synthesis and thermal decomposition of a dibenzofulvene-O2 copolymer

  Nakano, Tamaki, Nakagawa, Osamu, Yade, Tohru

  Abstracts of Papers, 226th ACS National Meeting, New York, NY, United States 2003年 [査読有り][通常論文]
  
• Synthesis and thermal decomposition of a dibenzofulvene-O2 copolymer

  Nakano, Tamaki, Nakagawa, Osamu, Yade, Tohru

  PMSE Preprints 89 365  2003年 [査読有り][通常論文]
  
• Acrylic polymer and charge transport material

  Ishizawa, Hideaki, Nakano, Tamaki

  2003年 [査読有り][通常論文]
  
• Novel polyester having π-conjugated group in side chain and charge transporting material using the same

  Nakano, Tamaki

  2003年 [査読有り][通常論文]
  
• Heat-decomposable polymers

  Nakano, Tamaki

  2003年 [査読有り][通常論文]
  
• Optically active high-molecular compounds

  Nakano, Tamaki

  2003年 [査読有り][通常論文]
  
• Stereocontrol in radical polymerization of acrylic monomers

  Y Okamoto, S Habaue, Y Isobe, T Nakano

  MACROMOLECULAR SYMPOSIA 183 83 - 88 2002年07月 [査読有り][通常論文]
   

  A clear effect of Lewis acids, such as scandium trifluoromethanesulfonate [Sc(OTf)(3)], on stereocontrol during the radical polymerization of a designed monomer, benzyl (x(methoxy methyl)acrylate was found. This Lewis acid also influenced the stereochemistry in the radical polymerzation of methyl methacrylate giving a less syndiotactic and more isotactic polymer, although many Lewis acids were not effective. A catalytic amount of Lewis acids, such as Y(OTf)(3) and Yb(OTf)(3). also significantly enhanced isotactic-specificity during the radical polymerization of acrylamide and its derivatives. N-isopropylacrylamide (NIPAM) and N,N-dimethylacrylamide. Obvious solvent and temperature effects on tacticity were observed in these polymerizations, and poly(NIPAM) with >80% triad isotactic content has been obtained in the presence of Lewis acids.
• Synthesis of single-handed helical poly(1-dibenzosuberyl methacrylate) via radical polymerization in the presence of an optically active cobalt(II) complex

  T Nakano, K Tsunematsu, Y Okamoto

  CHEMISTRY LETTERS 1 42 - 43 2002年01月 [査読有り][通常論文]
   

  The radical polymerization of 1-phenyldibenzosuberyl methacrylate in the presence of an optically active cobalt(II) complex led to an optically active polymer having a single-handed helical conformation.
• Synthesis of single-handed helical polymethacrylates from designed bulky monomers by anionic and free radical catalyses

  Okamoto, Yoshio, Tsunematsu, Kumiko, Ueda, Kiyoko, Hidaka, Yasuaki, Kinjo, Naotaka, Nakano, Tamaki

  ACS Symposium Series 812 11 - 23 2002年 [査読有り][通常論文]
  
• Poly(vinyl alcohol) fibers and production methods therefor

  Okamoto, Yoshio, Nakano, Tamaki, Habagami, Shigeki, Sawamoto, Mitsuo, Kamigaito, Masami, Nagata, Naohiko, Nagae, Yoshitaka, Terada, Kazutoshi, Ootake, Tomiaki

  2002年 [査読有り][通常論文]
  
• Regulation of stereoregularity in radical polymerization of unsaturated carboxylic acids with metal Lewis acid catalysts

  Okamoto, Yoshio, Nakano, Tamaki, Habagami, Shigeki, Sawamoto, Mitsuo, Kamigaito, Masaki, Nagata, Naohiko, Nagae, Yoshitaka, Terada, Kazutoshi, Otake, Tomiaki, Okano, Yoshimichi

  2002年 [査読有り][通常論文]
  
• Synthesis of polydibenzofulvene having stacked π-electron systems, a new potential polymer for photonics and electronics

  Nakano, Tamaki, Yade, Tohru, Ishizawa, Hideaki, Nakagawa, Osamu, Okamoto, Yoshio

  Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) 43 2 609  2002年 [査読有り][通常論文]
  
• Synthesis of polydibenzofulvene having stacked π-electron systems: A new potential polymer for photonics and electronics

  Nakano, Tamaki, Yade, Tohru, Ishizawa, Hideaki, Nakagawa, Osamu, Okamoto, Yoshio

  Abstracts of Papers, 224th ACS National Meeting, Boston, MA, United States 2002年 [査読有り][通常論文]
  
• π-stacked polymer having unique optical property and solubility and polymerizable monomer therefor

  Nakano, Tamaki

  2002年 [査読有り][通常論文]
  
• Synthetic helical polymers: Conformation and function

  T Nakano, Y Okamoto

  CHEMICAL REVIEWS 101 12 4013 - 4038 2001年12月 [査読有り][通常論文]
  
• Dibenzofulvene, a 1,1-Diphenylethylene Analogue, Gives a π-Stacked Polymer by Anionic, Free-Radical, and Cationic Catalysts

  Nakano, Tamaki, Takewaki, Kazuyuki, Yade, Tohru, Okamoto, Yoshio

  Journal of the American Chemical Society 123 37 9182 - 9183 2001年09月 [査読有り][通常論文]
  
• Stereocontrol during the free-radical polymerization of methacrylates with Lewis acids

  Y Isobe, T Nakano, Y Okamoto

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 39 9 1463 - 1471 2001年05月 [査読有り][通常論文]
   

  The free-radical polymerizations of methyl methacrylate (MMA), ethyl methacrylate, isopropyl methacrylate, and 2-methoxyethyl methacrylate were carried out in the presence of various Lewis acids. The MMA polymerization in the presence of scandium trifluoromethanesulfonate [Sc(OTf)(3)] in toluene or CHCl3 produced a polymer with a higher isotacticity and heterotacticity than that produced in the absence of Sc(OTf)(3). Similar effects were observed during the polymerization of the other monomers. ScCl3, Yb(OTf)(3), Er(OTf)(3), HfCl4, HfBr4, and In(OTf)(3) also increased the isotacticity and heterotacticity of the polymers. The effects of the Lewis acids were greater in a solvent with a lower polarity and were negligible in tetrahydrofuran and N,N-dimethylformamide. Sc(OTf)(3) was also found to accelerate the polymerization of MMA. On the basis of an NMR analysis of a mixture of Sc(OTf)(3), MMA, and poly(methyl methacrylate), the monomer-Sc(OTf)(3) interaction seems to be involved in the stereochemical mechanism of the polymerization. (C) 2001 John Wiley & Sons, Inc.
• Synthesis and chiral recognition ability of a cross-linked polymer gel prepared by a molecular imprint method using chiral helical polymers as templates

  T Nakano, Y Satoh, Y Okamoto

  MACROMOLECULES 34 8 2405 - 2407 2001年04月 [査読有り][通常論文]
  
• Asymmetric Anionic and Free-Radical Polymerization of 10,10-Dimethyl-and 10,10-Dibutyl-9-pheny1-9,10-dihydroanthracen-9-yl Methacrylate Leading to Single-Handed Helical Polymers

  NAKANO Tamaki, KINJO Naotaka, HIDAKA Yasuaki, OKAMOTO Yoshio

  Polymer journal 33 3 306 - 309 Society of Polymer Science 2001年03月15日 [査読無し][通常論文]
  
• Selective skeletal rearrangement of bicyclo[n.2.0] ketones to bridged medium-ring compounds

  Kakiuchi, Kiyomi, Morimoto, Tsumoru, Tsutsumi, Ken, Nakano, Tamaki

  Abstracts of Papers, 221st ACS National Meeting, San Diego, CA, United States 2001年 [査読有り][通常論文]
  
• Asymmetric anionic and free-radical polymerization of 10,10-dimethyl- and 10,10-dibutyl-9-phenyl-9,10-dihydroanthracen-9-yl methacrylate leading to single-handed helical polymers

  T Nakano, N Kinjo, Y Hidaka, Y Okamoto

  POLYMER JOURNAL 33 3 306 - 309 2001年 [査読有り][通常論文]
  
• Optically active methacrylate polymers with high isotacticity and their preparation

  Okamoto, Yoshio, Nakano, Tamaki

  2001年 [査読有り][通常論文]
  
• Piperidine group-containing methacrylic acid ester, their preparation, and polymers therefrom with high stereoregularity

  Okamoto, Yoshio, Nakano, Tamaki

  2001年 [査読有り][通常論文]
  
• Helix-sense-selective polymerization of (1-methylpiperidin-4-yl)diphenylmethyl methacrylate by anionic and free-radical catalysis

  Nakano, Tamaki, Ueda, Kiyoko, Okamoto, Yoshio

  Journal of Polymer Science, Part A: Polymer Chemistry 39 10 1610 - 1614 2001年 [査読有り][通常論文]
  
• Manufacture of highly syndiotactic vinyl alcohol polymers

  Okamoto, Yoshio, Nakano, Tamaki, Sawamoto, Mitsuo, Kamigaito, Masaki, Nagata, Naohiko, Nagae, Yoshitaka, Yamada, Kazunobu, Terada, Kazutoshi, Otake, Tomiaki, Kanesaka, Junichiro

  2001年 [査読有り][通常論文]
  
• Asymmetric radical polymerization

  T Nakano

  KOBUNSHI RONBUNSHU 58 8 411 - 426 2001年 [査読有り][通常論文]
   

  Methods of chiral induction were found for radical polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) and for those of N-phenyl- and N-cyclohexylmaleimide (PMI and CHMI). PDBSMA gives an almost completely isotactic polymer by conventional radical polymerization; the product is an equimolar mixture of right- and left-handed helices. Helix-sense selection during the radical polymerization of PDBSMA was realized using optically active peroxides as initiators, thiols as chain-transfer agents (CTA), alcohols as solvents, and cobalt (II) complexes as additives. When the first three chiral sources were used, helix-sense selection took place through termination reactions, i.e. primary radical termination or hydrogen transfer from CTA or solvent to the growing radical. Though the chiral induction mechanism of cobalt (II) is not completely clear, the complex seems to interact with the growing radical. Polymers of PMI and CHMI may contain achiral cis- and chiral trans-monomeric units in the main-chain. Polymerization of the two monomers in the presence of an optically active cobalt (II) complex led to optically active polymers. Through an interaction between the cobalt (II) species and growing radical, either (R,R)- or (S,S)- form of the trans-unit may have been produced in excess.
• Electron spin resonance study of stereospecific polymerization of vinyl esters in fluoroalcohols

  K Yamada, A Kajiwara, T Nakano, Y Okamoto

  POLYMER JOURNAL 33 3 313 - 316 2001年 [査読無し][通常論文]
  
• Stereospecific polymerization of vinyl acetate in fluoroalcohols and synthesis of syndiotactic poly(vinyl alcohol)

  Y Nagara, K Yamada, T Nakano, Y Okamoto

  POLYMER JOURNAL 33 7 534 - 539 2001年 [査読無し][通常論文]
   

  The free-radical polymerization of vinyl acetate (VAc) was carried out in various alcoholic solvents in connection with our recent publication in which we reported that the radical polymerization of VAc in (CF3)(3)COH as a solvent results in a polymer having a high syndiotacticity (r = 72.2%) [K. Yamada, T. Nakano, and Y. Okamoto, Macromolecules, 31, 7598 (1998)]. In this study, (CF3)(2)CHOH. a fluoroalcohol much less expensive than (CF3)(3)COH, was found to have an r-enhancing effect similar to (CF3)(3)COH. The syndiotacticity achieved in this system was up to 70.3%, which is comparable to that during the radical polymerization of vinyl esters in (CF3)3COH. Through the large scale polymerization using (CF3)(2)CHOH as a solvent, syndiotactic PVA (r = 69.2%) was obtained for the characterization of its physical properties. It is noteworthy that the polymerization in (CF3)2CHOH at -78 degreesC smoothly proceeded in spite of the fact that the reaction system was apparently solid.
• Stereospecific Radical Polymerization of N-Methyl Methacrylamid

  ZHANG Jing, LIU Weihong, NAKANO Tamaki, OKAMOTO Yoshio

  Polymer journal 32 8 694 - 699 Society of Polymer Science 2000年08月15日 [査読無し][通常論文]
  
• Asymmetric polymerization of methacrylates

  T Nakano, Y Okamoto

  MACROMOLECULAR RAPID COMMUNICATIONS 21 10 603 - 612 2000年07月 [査読有り][通常論文]
   

  The syntheses of optically active polymers having helical conformation from bulky methacrylates are reviewed focusing on selected topics. The monomers include triphenylmethyl methacrylate and its analogues. Asymmetric anionic polymerization of the monomers gives isotactic, optically active polymers having a helical structure with excess helicity, The isotactic content and the extent of helical-sense excess depend on the monomer structure and the reaction conditions. In the case of methacrylates, completely isotactic and single-handed helical polymers can be produced by asymmetric anionic polymerization (helix-sense-selective polymerization). Asymmetric radical polymerization is also possible for this class of monomer. Some of the helical polymers show chiral recognition ability coward a wide range of racemic compounds. Polymers having main-chain configurational chirality are also discussed.
• Polymerization of t-butyl acrylate using organoaluminum complexes and correlation between main-chain tacticity and glass transition temperature of the obtained polymers

  WH Liu, T Nakano, Y Okamoto

  POLYMER 41 12 4467 - 4472 2000年06月 [査読有り][通常論文]
   

  The polymerization of tert-butyl acrylate (tBA) was performed with triethylaluminum-(-)-sparteine, triethylaluminum-tertiary phosphine, triethylaluminum-n-BuLi and bis(2,6-di-tert-butyl-4-methylphenoxide)methylaluminium-t-BuLi complexes in toluene. The poly (tBA)s obtained with these initiators were rich in syndiotactic diad as observed by H-1 NMR analysis. On the basis of the triad and tetrad stereochemical information of the poly(tBA)s obtained using triethylaluminum-(-)-sparteine and triethylaluminum-n-BuLi, the polymerization reactions were found to obey Bernoullian statistics. Glass transition temperatures of the poly(tBA)s were measured by differential scanning calorimetry (DSC). A syndiotactic poly(tBA) (racemo (r) diad content: 65%) and an isotactic one (r = 19%) exhibited higher glass transition temperature (50 and 43 degrees C, respectively) than an atactic one (r = 50%, T-g = 21 degrees C). (C) 2000 Elsevier Science Ltd. All rights reserved.
• Asymmetric radical polymerization of maleimides using a chiral cobalt(II) complex

  T Nakano, D Tamada, J Miyazaki, K Kakiuchi, Y Okamoto

  MACROMOLECULES 33 5 1489 - 1491 2000年03月 [査読有り][通常論文]
  
• Stereospecific radical polymerization of fluoroalkyl acrylates

  WH Liu, T Nakano, Y Okamoto

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 6 1024 - 1032 2000年03月 [査読有り][通常論文]
   

  The free-radical polymerization of 2,2,2-trifluoroethyl acrylate (TFEA), 1,1,1,3,3,3-hexafluoro-2-propyl acrylate (HFiPA) and perfluoro-tert-butyl acrylate (PFtBA) was carried out under various conditions and the stereostructure of the obtained polymers was investigated. Most polymerizations of the three monomers afforded polymers rich in diad syndiotacticity (r) in bulk or in solution; the r-specificity was higher in the HFiPA and PFtBA polymerization than in the TFEA polymerization. Although the tacticity was nearly independent of reaction temperature during the polymerization of TFEA, the r-specificity increased by lowering the reaction tempera -ture during the polymerization of the other two monomers. The polymerization stereochemistry was also affected by the reaction solvents including toluene, tetrahydrofuran, and fluoroalcohols. It was noted that the stereochemistry of the polymerization of HFiPA and PFtBA also depended on the monomer concentration, and a lower monomer concentration led to a higher r-specificity. By optimizing the aforementioned reaction conditions, the poly(HFiPA) having r = 81% (polymerization in tetrahydrofuran at -98 degrees C at [M](o) = 0.2M) and the poly(PFtBA) having r = 77% (polymerization in toluene at -78 degrees C at [M](o) = 0.2M) were obtained. (C) 2000 John Wiley & Sons, Inc.
• Free-radical copolymerization of vinyl esters using fluoroalcohols as solvents: The solvent effect on the monomer reactivity ratio

  K Yamada, T Nakano, Y Okamoto

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 1 220 - 228 2000年01月 [査読有り][通常論文]
   

  Free-radical copolymerizations of vinyl acetate (VAc = M-1) and other vinyl esters (= M-2) including vinyl pivalate (VPi), vinyl 2,2-bis(trifluoromethyl)propionate (VF6Pi), and vinyl benzoate (VBz) with fluoroalcohols and tetrahydrofuran (THF) as the solvents were investigated. The fluoroalcohols affected not only the stereochemistry but also the polymerization rate. The polymerization rate was higher in the fluoroalcohols than in THF. The accelerating effect of the fluoroalcohols on the polymerization was probably due to the interaction of the solvents with the ester side groups of the monomers and growing radical species. The difference in the monomer reactivity ratios (r(1), r(2)) in THF and 2,2,2-trifluoroethanol was relatively small for all reaction conditions and for the monomers tested in this work, whereas r(1) increased in the VAc-VF6Pi copolymerization and r(2) decreased in the VAc-VPi copolymerization when perfluorotert-butyl alcohol was used as the solvent. These results were ascribed to steric and monomer-activating effects due to the hydrogen bonding between the monomers and solvents. (C) 2000 John Wiley & Sons, Inc.
• Manufacture of polyvinyl alcohol with high heterotacticity in branched fluoroalcohol solvents

  Yamada, Kazunobu, Okamoto, Yoshio, Nakano, Tamaki, Sawamoto, Mitsuo, Kitabatake, Kazutsugu, Terada, Kazutoshi, Ida, Hirotsugu, Kano, Yoshiaki, Oki, Hiroyoshi, Okano, Yoshimichi

  Yamada, Kazunobu; Okamoto, Yoshio; Nakano, Tamaki; Sawamoto, Mitsuo; Kitabatake, Kazutsugu; Terada, Kazutoshi; Ida, Hirotsugu; Kano, Yoshiaki; Oki, Hiroyoshi; Okano, Yoshimichi 2000年 [査読有り][通常論文]
  
• Control of stereoregularity in radical polymerization and manufacture of stereoregular acrylic polymers by the method

  Yamada, Kazunobu, Isobe, Yutaka, Okamoto, Yoshio, Nakano, Tamaki, Sawamoto, Mitsuo, Kitahata, Kazutsugu, Terada, Kazutoshi, Ida, Hirotsugu, Okano, Yoshimichi, Nishimura, Masamichi

  2000年 [査読有り][通常論文]
  
• Synthesis of single-handed helical polymethacrylates from designed bulky monomers by anionic and free-radical catalyses

  Okamoto, Yoshio, Ueda, Kiyoko, Kinjo, Naotaka, Nakano, Tamaki

  Polymer Preprints 41 1 887 - 888 2000年 [査読有り][通常論文]
  
• Manufacture of optically active crosslinked gel with solvolysis resistance and excellent optical property

  Okamoto, Yoshio, Nakano, Tamaki

  2000年 [査読有り][通常論文]
  
• Synthesis of single-handed helical polymethacrylates from designed-bulky monomers by anionic and free-radical catalyses

  Okamoto, Yoshio, Ueda, Kiyoko, Kinjo, Naotaka, Nakano, Tamaki

  Book of Abstracts, 219th ACS National Meeting, San Francisco 2000年 [査読有り][通常論文]
  
• Chiral induction in radical polymerization of maleimide derivatives using optically active cobalt(II) complexes

  Nakano, Tamaki, Tamada, Daisuke, Kakiuchi, Kiyomi, Okamoto, Yoshio

  Polymer Preprints (American Chemical Society, Division of Polymer Chemistry) 41 2 1229 - 1230 2000年 [査読有り][通常論文]
  
• Stereospecific radical polymerization of N-methyl methacrylamide

  J Zhang, WH Liu, T Nakano, Y Okamoto

  POLYMER JOURNAL 32 8 694 - 699 2000年 [査読有り][通常論文]
   

  N-Methyl methacrylamide (N-MMAm) was polymerized using radical initiators under various conditions. The triad tacticity of the obtained polymers was determined by 100 MHz C-13 NMR. The polymers were rich in syndiotactic configuration. At a given temperature, the syndiotacticity increased with an increase in solvent polarity. This solvent effect may have connection with the hydrogen bonding interaction among solvent, monomer, and growing species. The fraction of rr triad increased with decreasing polymerization temperature in all solvents. Monomer concentration also affected the stereochemistry of the polymerization. By optimizing conditions, a high rr specificity (rr = 95%) was achieved. Thermal property of the poly(N-MMAm)s with different tacticities was studied by DSC.
• Stereochemistry in radical polymerization of vinyl esters

  Okamoto, Yoshio, Yamada, Kazunobu, Nakano, Tamaki

  ACS Symposium Series 768 57 - 67 2000年 [査読有り][通常論文]
  
• Stereocontrol in radical polymerization of N,N-dimethylacrylamide and N,N-diphenylacrylamide and thermal properties of syndiotactic poly(methyl acrylate)s derived from the obtained polymers

  WH Liu, T Nakano, Y Okamoto

  POLYMER JOURNAL 32 9 771 - 777 2000年 [査読有り][通常論文]
   

  Free-radical polymerizations of N,N-dimethylacrylamide (DMAA) and N,N-diphenylacrylamide (DPAA) were carried out under various conditions. DMAA gave an isotactic-rich polymer in most cases, whereas DPAA gave a syndiotactic polymer. The polymerization stereochemistry was also affected by reaction solvents including toluene, tetrahydrofuran, and fluoroalcohols. It is notable that the stereochemistry of the polymerization depended on monomer concentration: a lower monomer concentration led to a higher isotacticity for DMAA polymerization and a higher syndiotacticity for DPAA polymerization. This effect was explained by assuming that there exist two types of growing radicals having different stereoselectivities. By optimizing the aforementioned reaction conditions, poly(DMAA) with diad isotacticity im) of 77% (polymerization in toluene at -78 degreesC at [M](o) = 0.1 M) and poly(DPAA) with diad syndiotacticity (r) Of 93% (polymerization in THF at -98 degreesC at [M](o) = 0.22 M) were obtained. Stereoregular poly(methyl acrylate)s were derived from the Doly(DPAA)s. Thermal property of the poly(methyl acrylate)s with different tacticities was studied by DSC.
• Asymmetric polymerization

  Okamoto, Yoshio, Nakano, Tamaki

  Catalytic Asymmetric Synthesis (2nd Edition) 757 - 796 2000年 [査読有り][通常論文]
  
• Chiral induction in radical polymerization of maleimide derivatives using optically active cobalt(II) complexes

  Nakano, Tamaki, Tamada, Daisuke, Miyazaki, Jun-ichi, Kakiuchi, Kiyomi, Okamoto, Yoshio

  Abstracts of Papers, 220th ACS National Meeting, Washington, DC, United States 2000年 [査読有り][通常論文]
  
• Free-radical polymerization

  nakano.tamaki

  Polymer Yearbook 17 361 - 366 2000年 [査読有り][通常論文]
  
• Stereocontrol in the free-radical polymerization of methacrylates with fluoroalcohols

  Y Isobe, K Yamada, T Nakano, Y Okamoto

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 Supplement 4693 - 4703 2000年 [査読有り][通常論文]
   

  The free-radical polymerization of methyl methacrylate (MMA), ethyl methacrylate (EMA), isopropyl methacrylate (IPMA), and tert-butyl methacrylate (t-BuMA) was carried out under various conditions to achieve stereoregulation. In the MMA polymerization, syndiotactic specificity was enhanced by the use of fluoroalcohols, including (CF3)(3)COH as a solvent or an additive. The polymerization of MMA in (CFs(3))(3)COH at -98 degreesC achieved the highest syndiotacticity (rr = 93%) for the radical polymerization of methacrylates. Similar effects of fluoroalcohols enhancing syndiotactic specificity were also observed in the polymerization of EMA, whereas the effect was negligible in the IPMA polymerization. In contrast to the polymerizations of MMA and EMA, syndiotactic specificity was decreased by the use of (CF3)(3)COH in the t-BuMA polymerization. The stereoeffects of fluoroalcohols seemed to be due to the hydrogen-bonding interaction of the alcohols with monomers and growing species. The interaction was confirmed by NMR measurements. In addition, in the bulk polymerization of MMA at -78 degreesC, syndiotactic specificity and polymer yield increased even in the presence of a small amount {[(CF3)(3)COH]/[MMA](0) < 1] of (CF3)(3)COH. (C) 2000 John Wiley & Sons, Inc.
• Stereochemistry of radical polymerization of vinyl esters in the presence of Lewis acid

  K Yamada, T Nakano, Y Okamoto

  POLYMER JOURNAL 32 8 707 - 710 2000年 [査読無し][通常論文]
  
• Stereocontrol in radical polymerization of N,N-dimethylacrylamide and N,N-diphenylacrylamide and thermal properties of syndiotactic poly(methyl acrylate)s derived from the obtained polymers

  WH Liu, T Nakano, Y Okamoto

  POLYMER JOURNAL 32 9 771 - 777 2000年 [査読無し][通常論文]
   

  Free-radical polymerizations of N,N-dimethylacrylamide (DMAA) and N,N-diphenylacrylamide (DPAA) were carried out under various conditions. DMAA gave an isotactic-rich polymer in most cases, whereas DPAA gave a syndiotactic polymer. The polymerization stereochemistry was also affected by reaction solvents including toluene, tetrahydrofuran, and fluoroalcohols. It is notable that the stereochemistry of the polymerization depended on monomer concentration: a lower monomer concentration led to a higher isotacticity for DMAA polymerization and a higher syndiotacticity for DPAA polymerization. This effect was explained by assuming that there exist two types of growing radicals having different stereoselectivities. By optimizing the aforementioned reaction conditions, poly(DMAA) with diad isotacticity im) of 77% (polymerization in toluene at -78 degreesC at [M](o) = 0.1 M) and poly(DPAA) with diad syndiotacticity (r) Of 93% (polymerization in THF at -98 degreesC at [M](o) = 0.22 M) were obtained. Stereoregular poly(methyl acrylate)s were derived from the Doly(DPAA)s. Thermal property of the poly(methyl acrylate)s with different tacticities was studied by DSC.
• Stereospecific free-radical polymerization of methacrylates using fluoroalcohols as solvents

  Y Isobe, K Yamada, T Nakano, Y Okamoto

  MACROMOLECULES 32 18 5979 - 5981 1999年09月 [査読有り][通常論文]
  
• Polymerization of optically active 2-fluorophenyl-4-fluorophenyl-2-pyridylmethyl methacrylate with anionic and radical initiators: Stereospecificity and helix-sense selection

  J Wu, T Nakano, Y Okamoto

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 37 14 2645 - 2648 1999年07月 [査読有り][通常論文]
   

  Almost optically pure (+)- and (-)-2-fluorophenyl-4-fluorophenyl-2-pyridylmethyl methacrylate (2F4F2PyMA) monomers were obtained by HPLC resolution of the racemic monomer and polymerized with the use of anionic and free-radical initiators. Helix-sense selectivity during the polymerization seemed to be governed mainly by the chirality of the monomer itself, and the polymers obtained by using the complex of N,N'-diphenylethylenediamine monolithium amide with(S)-(+)-1-(2-pyrrolidinylmethyl)-pyrrolidine (PMP) in toluene at -78 degrees C appeared to possess single-handed helical conformation (+)-poly[(-)-2F4F2PyMA], [alpha](365) + 1510 degrees; (-)-poly[(+)-2F4F2PyMA], [alpha](365) - 1610 degrees]. The single-handed helical (+)-poly[(-)-2F4F2PyMA] and (-)-poly[(+)-2F4F2PyM] obtained with the PMP complex exhibited better chiral recognition ability toward trans-stilbene oxide compared with the single-handed helical poly(rac-2F4F2PyMA) prepared previously. (C) 1999 John Wiley & Sons, Inc.
• Free-radical polymerization of vinyl esters using fluoroalcohols as solvents: Effect of monomer structure on stereochemistry

  K Yamada, T Nakano, Y Okamoto

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 37 14 2677 - 2683 1999年07月 [査読有り][通常論文]
   

  Free-radical polymerization of vinyl esters including vinyl propionate (VPr), vinyl isobutylate (ViBu), vinyl 2,2-dimethylbutylate (VDMB), vinyl 2,2-dimethylvalerate (VDMV), vinyl 2,2-bis(trifluoromethyl)propionate (VF6Pi), and vinyl benzoate (VBz) was carried out using fluoroalcohols as solvents, and the tacticity of the obtained polymers was determined by NMR analysis of the produced poly(vinyl alcohol) (PVA). The polymerization of VPr, ViBu, VDMB, and VDMV, which are bulkier than VAc, in fluoroalcohols afforded polymers rich in heterotacticity (up to mr = 61%) similar to that of vinyl pivalate (VPi) whereas VAc is known to give a syndiotactic polymer under the reaction conditions used here. The polymerization of VF6Pi, which is the bulkiest among the monomers used in this study, gave a polymer rich in syndiotacticity in bulk and in fluoroalcohols regardless of the structure of the solvents. On the other hand, the polymerization of VBz in fluoroalcohols gave olymers with a higher isotacticity (up to mm = 33%) than bulk polymerization. Thus the monomer structure strongly affected the stereochemistry of the free-radical polymerization of vinyl esters in fluoroalcohols. (C) 1999 John Wiley & Sons, Inc.
• フルオロアルコール中でのビニルエステルのラジカル重合における立体制御

  山田 和信, 中野 環, 岡本 佳男

  高分子 48 7 512 - 512 公益社団法人 高分子学会 1999年07月01日 [査読無し][通常論文]
  
• Quaternary salt formation of optically active helical polymethacrylates having pyridyl group in the side chain

  T Nakano, Y Satoh, Y Okamoto

  REACTIVE & FUNCTIONAL POLYMERS 40 2 135 - 141 1999年05月 [査読有り][通常論文]
   

  The reaction of diphenyl-3-pyridylmethyl and 1-(3-pyridyl)dibenzosuberyl methacrylates with CH3I in CHCl3 at 35 degrees C for 24 h lead to quantitative quaternization of pyridyl group while the reaction using diphenyl-2-pyridylmethyl and 1-(2-pyridyl)dibentosuberyl methacrylates gave only low degree of quaternization. Single-handed helical poly(diphenyl-3-pyridylmethyl) and poly[1-(3-pyridyl)dibenzosuberyl methacrylate] were also quantitatively quaternized with CH3I under the above reaction conditions: the former polymer appeared to lose its helical conformation and the chiroptical properties through the reaction while the conformation of the latter polymer seems to sun;ive the quaternization process. The latter polymer quantitatively reacted with decyl and octadecyl iodides in a CHCl3-DMSO mixture at 55 degrees C to give hairy rod molecules. (C) 1999 Elsevier Science B.V. All rights reserved.
• Helix-sense-selective free-radical polymerization of 1-phenyldibenzosuberyl methacrylate using a cobalt(II) complex

  T Nakano, Y Okamoto

  MACROMOLECULES 32 7 2391 - 2393 1999年04月 [査読有り][通常論文]
  
• Stereoregulation in free-radical polymerizaion of methacrylates

  Okamoto, Yoshio, Nakano, Tamaki, Yamada, Kazunobu, Isobe, Yutaka

  Book of Abstracts, 217th ACS National Meeting, Anaheim, Calif 1999年 [査読有り][通常論文]
  
• Stereoregulation in free-radical polymerization of methacrylates

  Okamoto, Yoshio, Nakano, Tamaki, Yamada, Kazunobu, Isobe, Yutaka

  Polymeric Materials Science and Engineering 80 83  1999年 [査読有り][通常論文]
  
• Optically active methacrylate ester polymers, their preparation, and optical resolution agents

  Okamoto, Yoshio, Nakano, Tamaki

  1999年 [査読有り][通常論文]
  
• (Halophenyl)pyridylmethyl methacrylates, their manufacture, optical resolution, and manufacture of their polymers as optical resolution agents

  Okamoto, Yoshio, Nakano, Tamaki, Wu, Jian

  1999年 [査読有り][通常論文]
  
• Manufacture of highly syndiotactic poly(vinyl alcohol)

  Yamada, Kazunobu, Okamoto, Yoshio, Nakano, Tamaki, Sawamoto, Mitsuo, Nakajima, Hiroshi, Terada, Kazutoshi, Ita, Hirotsugu, Asahi, Tetsuya, Oki, Akiyoshi, Okano, Yoshimichi

  1999年 [査読有り][通常論文]
  
• Manufacture of poly(vinyl alcohols) with enhanced syndiotacticity

  Yamada, Kazunobu, Okamoto, Yoshio, Nakano, Tamaki, Sawamoto, Mitsuo, Nakajima, Hiroshi, Terada, Kazutoshi, Ida, Hirotsugu, Asahi, Tetsuya, Oki, Yoshiki, Okano, Yoshimichi

  1999年 [査読有り][通常論文]
  
• Stereocontrol in radical polymerization of vinyl esters in fluoroalcohols

  Yamada, Kazunobu, Nakano, Tamaki, Okamoto, Yoshio

  Kobunshi 48 7 512 - 512 公益社団法人 高分子学会 1999年 [査読有り][通常論文]
  
• Stereochemistry in radical polymerization of vinyl esters

  Okamoto, Yoshio, Nakano, Tamaki, Yamada, Kazunobu

  Book of Abstracts, 218th ACS National Meeting, New Orleans 1999年 [査読有り][通常論文]
  
• Stereochemistry in radical polymerization of vinyl esters

  Okamoto, Yoshio, Nakano, Tamaki, Yamada, Kazunobu

  Polymer Preprints 40 2 299 - 300 1999年 [査読有り][通常論文]
  
• Construction and control of helix structure

  Nakano, Tamaki

  Kagaku 54 11 65 - 66 1999年 [査読有り][通常論文]
  
• Stereochemistry of acrylate polymerization in toluene using n-BuLi

  WH Liu, T Nakano, Y Okamoto

  POLYMER JOURNAL 31 5 479 - 481 1999年 [査読無し][通常論文]
  
• Helix-sense-selective and enantiomer-selective polymerization of a chiral methacrylate by anionic and free-radical mechanisms

  T Nakano, N Kinjo, Y Hidaka, Y Okamoto

  POLYMER JOURNAL 31 5 464 - 469 1999年 [査読無し][通常論文]
   

  (+/-)-10.11-O-Isopropylidene-trans-10,11-dihydroxy-5-phenyl-10,11-dihydro-5H-dibenzo[a,d]cycloheptene- 5-yl methacrylate (IDPDMA) was synthesized and resolved into an optically pure form by chiral HPLC. Anionic polymerization of IDPDMA was carried out using the complexes of N,N'-diphenylethylenediamine monolithium amide (DPEDA-Li) with (+)-1-(2-pyrrolidinylmethyl)pyrrolidine. (+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane, and (-)-sparteine in toluene at - 78 degrees C or using DPEDA-Li in tetrahydrofuran at - 78 degrees C. The polymers obtained from the racemic monomer using the chiral initiators and the polymer obtained from (+)-monomer under the achiral condition appeared to have a helical conformation with excess helicity. The polymerizations of (+/-)-IDPDMA using the chiral initiators were enantiomer-selective: (+)-monomer was preferentially polymerized. Free-radical polymerization of optically active IDPDMA having various enantiomeric excesses using alpha,alpha-azobisisobutyronitrile in toluene at 60 degrees C gave almost completely isotactic polymers which probably had a helical conformation with excess helicity. Enantiomer selection was also confirmed in the radical polymerization.
• Stereospecific free radical polymerization of vinyl esters using fluoroalcohols as solvents

  K Yamada, T Nakano, Y Okamoto

  MACROMOLECULES 31 22 7598 - 7605 1998年11月 [査読有り][通常論文]
   

  Solvent effects on the stereochemistry of free radical polymerization of vinyl acetate (VAc) and vinyl pivalate (VPi) were investigated. In the polymerization of VAc, an alcoholic solvent with a smaller pK(a) and higher bulkiness afforded a polymer having a higher syndiotacticity. The polymerization of VAc in perfluoro-tert-butyl alcohol ((CF3)(3)COH) at -78 degrees C led to a diad syndiotacticity r of 72%, which is the highest for the radical polymerization of vinyl esters. On the other hand, the polymerization of VPi in fluoroalcohol at a low temperature afforded a polymer rich in heterotacticity (up to mr = 61%). Synthesis of a heterotactic homopolymer by the free radical polymerization of monosubstituted vinyl monomers is unprecedented. The stereochemical effects observed in this study may be due to hydrogen-bond interaction between the fluoroalcohol molecules and the ester groups of the vinyl ester monomer and the side chain of the growing polymer, Mechanisms of stereoregulation were proposed.
• Asymmetric anionic polymerization of (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl) methyl methacrylate leading to a helical polymer

  J Wu, T Nakano, Y Okamoto

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 36 12 2013 - 2019 1998年09月 [査読有り][通常論文]
   

  A novel racemic methacrylate, (2-fluorophenyl)( 4-fluorophenyl)( 2-pyridyl)-methyl methacrylate(1) (2F4F2PyMA), was synthesized and polymerized with chiral complexes of N,N'-diphenylethylenediamine monolithium amide (DPEDA-Li) with (-)-sparteine (Sp), (2S, 3S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)bu (DDB), and (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine (PMP) in toluene at -78 degrees C. The monomer showed higher resistance against methanolysis compared with triphenylmethyl methacrylate (TrMA) and several other analogues. In the asymmetric anionic polymerization of 2F4F2PyMA, PMP was found to be a more effective chiral ligand than DDB and Sp and gave quantitatively an optically active polymer with nearly perfect isotacticity. Enantiomer selection was observed in the polymerization of racemic 2F4F2PyMA with the chiral lithium complexes. Chiral recognition ability of the optically active poly( 2F4F2PyMA) was examined by an enantioselective adsorption experiment. (C) 1998 John Wiley & Sons, Inc.
• Stereospecific polymerization of vinyl acetate in fluoroalcohols - Synthesis of syndiotactic poly(vinyl alcohol)

  K Yamada, T Nakano, Y Okamoto

  PROCEEDINGS OF THE JAPAN ACADEMY SERIES B-PHYSICAL AND BIOLOGICAL SCIENCES 74 3 46 - 49 1998年03月 [査読有り][通常論文]
   

  The free-radical polymerization of vinyl acetate (VAc) was carried out in various alcoholic solvents. Fluoroalcohols with a lower pKa and higher bulkiness were effective in enhancing the syndiotactic specificity of the polymerization. The polymerization of VAc in perfluoro-tert-butyl alcohol ((CF3)(3)COH) at -78 degrees C led to a dyad syndiotacticity of 72%, which is the highest value reported for the radical polymerization of vinyl esters. Hydrogen-bonding between the acetyl groups of VAc and polymer and the fluoroalcohol molecule may be responsible for the enhancement of the syndiotactic specific propagation.
• Stereochemical control of free-radical polymerization of vinyl monomers

  Nakano, Tamaki, Okamoto, Yoshio

  ACS Symposium Series 685 ACS Symposium Series 451 - 462 1998年 [査読有り][通常論文]
  
• Stereospecific polymerization process of methacrylic acid or their derivatives using amine derivatives

  Okamoto, Yoshio, Nakano, Tamaki

  1998年 [査読有り][通常論文]
  
• symmetric polymerization of 9-phenylfluoren-9-yl methacrylate leading to a polymer with main-chain configurational chirality. Synthesis of optically active poly(methyl methacrylate)

  Nakano, Tamaki, Hidaka, Yasuaki, Okamoto, Yoshio

  Polymer Journal 30 7 596 - 600 1998年 [査読有り][通常論文]
  
• Asymmetric polymerization of 1-(3-pyridyl)dibenzosuberyl methacrylate and chiral recognition by the obtained optically active polymer having single-handed helical conformation

  T Nakano, Y Satoh, Y Okamoto

  POLYMER JOURNAL 30 8 635 - 640 1998年 [査読有り][通常論文]
   

  1-(3-Pyridyl)dibenzosuberyl methacrylate was synthesized and polymerized using the complexes of N,N'-diphenylethylenediamine monolithium amide with (+)-1-(2-pyrrolidinylmethyl)pyrrolidine, (+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane, and (-)-sparteine in toluene at -78 degrees C. The polymers obtained by the helix-sense-selective anionic polymerization were highly isotactic and exhibited large dextrorotation based on single-handed helical conformation. Free-radical polymerization in toluene with (iso-PrOCOO)(2) at 40 degrees C and with alpha,alpha'-azobisisobutyronitrile at 60 degrees C gave nearly perfectly isotactic polymers. The optically active polymer exhibited chiral recognition ability toward trans-stilbene oxide and Triiger's base as revealed by chiral adsorption experiments.
• Synthesis of syndiotactic poly(vinyl alcohol) from fluorine-containing vinyl esters

  K Yamada, T Nakano, Y Okamoto

  POLYMER JOURNAL 30 8 641 - 645 1998年 [査読有り][通常論文]
   

  Radical polymerization of vinyl pivalate (VPi), vinyl trifluoroacetate (VTFAc), vinyl 2,2-bis(trifluoromethyl)propionate (1), vinyl 5H-octafluorovalerate (2), vinyl 7H-dodecafluoroheptanoate (3), and vinyl 9H-hexadecafluorononanoate (4) was carried out and the tacticity of the resulting polymers was determined by H-1 or C-13 NMR analysis of poly(vinyl alcohol) (PVA) derived from the original polymers. In the bulk polymerization at 60 degrees C, the order of diad syndiotacticity of the polymers was poly(VTFAc) (57%) <poly(VPi) (60%) <poly-2, poly-3, poly-4 (61-62%) < poly-1 (65%), suggesting that steric and electrostatic effects of the fluorine-containing side groups of monomers influence the syndiotactic specificity of propagation reaction. A syndiotacticity of 69% was achieved by solution polymerization of 1 in tetrahydrofuran at 0 degrees C. This is the highest syndiotacticity reported for the radical polymerization of vinyl esters at 0 degrees C or higher temperatures. The difference of activation enthalpy (Delta H double dagger) and activation entropy (Delta S double dagger) between isotactic and syndiotactic propagations in bulk polymerization of 1 were estimated to be 460 cal mol(-1) and 0.2 cal deg(-1) mol(-1), respectively. Solvolysis rates of the vinyl esters and their polymers were also examined.
• Stereochemistry of free-radical polymerization of bulky vinyl esters

  T Nakano, KI Makita, Y Okamoto

  POLYMER JOURNAL 30 8 681 - 683 1998年 [査読有り][通常論文]
  
• Asymmetric polymerization of 9-phenylfluoren-9-yl methacrylate leading to a polymer with main-chain configurational chirality. Synthesis of optically active poly(methyl methacrylate)

  T Nakano, Y Hidaka, Y Okamoto

  POLYMER JOURNAL 30 7 596 - 600 1998年 [査読無し][通常論文]
   

  Polymerization of 9-phenylfluoren-9-yl methacrylate was carried out aiming at obtaining highly isotactic, single-handed helical polymers using the complexes of N,N'-diphenylethylenediamine monolithium amide with (-)-sparteine, (+)-1-(2-pyrroiidinylmethyl)pyrrolidine, and (+)-2.3-dimethoxy-1,4-bis(dimethylamino)butane. Although the isotacticity (nun = 55-46%) and specific rotation ([alpha](365) -54- + 119 degrees) of the obtained polymers were much lower than those of known single-handed helical polymethacrylates, the poly(methyl methacrylate) (PMMA) derived from the obtained polymers exhibited rather high optical activity (Cal,cs -44--11 degrees) for a polymer which does not take any stable, chiral conformation. The optical activity of the PMMA was attributed to cofigurational chirality of the main chain.
• Synthesis of syndiotactic poly(vinyl alcohol) from fluorine-containing vinyl esters

  K Yamada, T Nakano, Y Okamoto

  POLYMER JOURNAL 30 8 641 - 645 1998年 [査読無し][通常論文]
   

  Radical polymerization of vinyl pivalate (VPi), vinyl trifluoroacetate (VTFAc), vinyl 2,2-bis(trifluoromethyl)propionate (1), vinyl 5H-octafluorovalerate (2), vinyl 7H-dodecafluoroheptanoate (3), and vinyl 9H-hexadecafluorononanoate (4) was carried out and the tacticity of the resulting polymers was determined by H-1 or C-13 NMR analysis of poly(vinyl alcohol) (PVA) derived from the original polymers. In the bulk polymerization at 60 degrees C, the order of diad syndiotacticity of the polymers was poly(VTFAc) (57%) <poly(VPi) (60%) <poly-2, poly-3, poly-4 (61-62%) < poly-1 (65%), suggesting that steric and electrostatic effects of the fluorine-containing side groups of monomers influence the syndiotactic specificity of propagation reaction. A syndiotacticity of 69% was achieved by solution polymerization of 1 in tetrahydrofuran at 0 degrees C. This is the highest syndiotacticity reported for the radical polymerization of vinyl esters at 0 degrees C or higher temperatures. The difference of activation enthalpy (Delta H double dagger) and activation entropy (Delta S double dagger) between isotactic and syndiotactic propagations in bulk polymerization of 1 were estimated to be 460 cal mol(-1) and 0.2 cal deg(-1) mol(-1), respectively. Solvolysis rates of the vinyl esters and their polymers were also examined.
• Asymmetric Polymerization of Dipheny1-3-pyridylmethyl Methacrylate Leading to Optically Active Polymer with Helical Conformation and Chiral Recognition Ability of the Polymer

  NAKANO Tamaki, TANIGUCHI Kyoichi, OKAMOTO Yoshio

  Polymer journal 29 6 540 - 544 Society of Polymer Science 1997年06月15日 [査読無し][通常論文]
  
• Stereoregulation and chiral induction by free radical polymerization

  Nakano, Tamaki

  Kobunshi 46 2 81  1997年 [査読有り][通常論文]
  
• Stereochemical control of free-radical polymerization of vinyl monomers.

  Nakano, Tamaki, Ishigaki, Y, Matsuda, A, Okamoto, Yoshio

  Polymer Preprints 38 1 764 - 765 1997年 [査読有り][通常論文]
  
• Asymmetric polymerization of diphenyl-3-pyridylmethyl methacrylate leading to optically active polymer with helical conformation and chiral recognition ability of the polymer

  T Nakano, K Taniguchi, Y Okamoto

  POLYMER JOURNAL 29 6 540 - 544 1997年 [査読有り][通常論文]
   

  Diphenyl-3-pyridylmethyl methacrylate was synthesized and polymerized using the complexes of N,N'-diphenylethylenediamine monolithium amide with (+)-1-(2-pyrrolidinylmethyl)pyrrolidine (+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane, and (-)-sparteine in toluene at -78 degrees C (helix-sense-selective polymerization). The obtained polymers were highly isotactic and exhibited large dextrorotation based on helical conformation with excess single-handed helicity. Free radical polymerization with (iso-PrOCOO)(2) in toluene at 40 degrees C also gave an isotactic polymer (mm similar to 74%). The optically active polymer exhibited chiral recognition ability toward several racemic compounds including hexahelicene, trans-stilbene oxide, and binaphthyl derivatives when adsorbed on macro porous silica gel and used as a stationary phase for high-performance liquid chromatography (HPLC).
• Radical polymerization of (meth)acrylic acid esters in presence of transition metal complexes

  Okamoto, Yoshio, Nakano, Tamaki

  1997年 [査読有り][通常論文]
  
• Synthesis and chiral recognition of helical polymers

  Y Okamoto, T Nakano, S Habaue, K Shiohara, K Maeda

  JOURNAL OF MACROMOLECULAR SCIENCE-PURE AND APPLIED CHEMISTRY A34 10 1771 - 1783 1997年 [査読有り][通常論文]
   

  Asymmetric syntheses of optically active polymethacrylate, polyacrylate, polyacrylamide, and polyisocyanate with helical conformation and their chiral recognition abilities are described. 1-Phenyldibenzosuberyl methacrylate (PDBSMA) gave a purely one-handed-helical, optically active polymer([alpha](365) + 1670 similar to + 1780 degrees) with almost perfectly isotactic structure by anionic polymerization using optically active initiators. Radical polymerizations of PDBSMA using chiral initiators, chain transfer agents, and additives also afforded optically active polymers with a prevailing one-handed helicity. Triphenylmethyl acrylate yielded an optically active, helical polymer ([alpha](365)+ 102 degrees) having a dyad isotacticity of 70% using an optically active anionic initiator. Although the polyacrylate demonstrated chiral recognition ability as a chiral stationary phase for HPLC, the ability was low mainly because of the low degree of one-handedness. N-(3 -Chlorophenyl)-N-phenylacrylamide gave an optically active, helical polymer ([alpha](365) - 343 degrees) in the asymmetric anionic polymerization; the polymer had a dyad tacticity of 77%. Optically active polyisocyanates with a predominantly one-handed helical conformation were prepared in homo and co-polymerization of optically active phenyl isocyanate derivative. These polyisocyanates showed the ability to discriminate enantiomers in solution.
• Helix-sense-selective free radical polymerization of 1-phenyldibenzosuberyl methacrylate

  T Nakano, Y Shikisai, Y Okamoto

  POLYMER JOURNAL 28 1 51 - 60 1996年 [査読有り][通常論文]
   

  The helix-sense-selective free radical polymerization of 1-phenyldibenzosuberyl methacrylate was carried out in toluene at 40 or 50 degrees C under chiral reaction conditions which involve (1) (-)-dimenthyl peroxydicarbonate and (-)-o-carbomenthoxybenzoyl peroxide as an initiator, (2) (-)- and (+)-menthol, (+)-neomenthol, and (+)-1-phenyl-1-butanol as a reaction solvent (additive), (3) (+)- and (-)-neomenthanethiol and (-)-menthanethiol as a chain transfer agent, and (4) (-)-phenyl-2-pyridyl-o-tolylmethyl methacrylate as a comonomer for copolymerization. Highly isotactic, optically active polymers having a helical conformation with excess light- or left-handed helicity were obtained, In the polymerization using an optically active initiator, helix-sense-selection appeared to lake place through primary radical termination. The helix-sense-selection in the polymerization in the presence of the optically active alcohols and thiols was found to involve chain transfer process. In polymerization using thiols, both hydrogen transfer reaction from a thiol to a growing radical and initiation by thio radical were suggested to be responsible for the selectivity. In the case of the copolymerization, the optically active monomeric unit incorporated into the polymer chain was found to induce excessive single handed helicity where the selected helicity reversed depending on the amount of the incorporated optically active monomeric units.
• Pronounced effects of temperature and monomer concentration on isotactic specificity of triphenylmethyl methacrylate polymerization through free radical mechanism. Thermodynamic versus kinetic control of propagation stereochemistry

  T Nakano, A Matsuda, Y Okamoto

  POLYMER JOURNAL 28 6 556 - 558 1996年 [査読有り][通常論文]
  
• Stereospecific and helix-sense-selective radical polymerization of methacrylates

  Okamoto, Yoshio, Nakano, Tamaki

  Polymer Preprints 37 2 444 - 445 1996年 [査読有り][通常論文]
  
• Optical resolution agents consisting of optically active methacrylate polymers

  Okamoto, Yoshio, Nakano, Tamaki

  1996年 [査読有り][通常論文]
  
• Helical polymers: synthesis, conformation, and function

  Okamoto, Yoshio, Nakano, Tamaki, Habaue, Shigeki

  New Macromolecular Architecture and Functions, Proceedings of the OUMS'95, 2nd, Toyonaka, Japan 89 - 98 1996年 [査読有り][通常論文]
  
• CYCLOPOLYMERIZATION OF OPTICALLY-ACTIVE (-)-TRANS-4,5-BIS((METHACRYLOYLOXY)DIPHENYL-METHYL)-2,2-DIMETHYL-1,3-DIOXACYCLOPENTANE THROUGH RADICAL AND ANIONIC MECHANISMS GIVES HIGHLY ISOTACTIC POLYMERS

  T NAKANO, Y OKAMOTO, DY SOGAH, SY ZHENG

  MACROMOLECULES 28 25 8705 - 8706 1995年12月 [査読有り][通常論文]
  
• HELIX-SENSE-SELECTIVE POLYMERIZATION OF 1-PHENYLDIBENZOSUBERYL METHACRYLATE BY FREE-RADICAL MECHANISM

  T NAKANO, Y SHIKISAI, Y OKAMOTO

  PROCEEDINGS OF THE JAPAN ACADEMY SERIES B-PHYSICAL AND BIOLOGICAL SCIENCES 71 8 251 - 255 1995年10月 [査読有り][通常論文]
   

  Free radical polymerization of 1-phenyldibenzosuberyl methacrylate was carried out in toluene at 40 or 50 degrees C under chiral reaction conditions based on the use of (-)-dimenthyl peroxydicarbonate as an initiator, (-)- and (+)-menthol as a reaction solvent (additive), and (+)- and (-)-neomenthanethiol as a chain transfer agent. The obtained polymers had a highly isotactic and helical structure; there was an excess of right- or left-handed helicity by the influence of the above chiral materials and consequently, the polymers were optically active. The mechanism of chiral induction for the polymerization using the chiral initiator involved helix-sense-selective primary radical termination, i.e., the reaction between a polymer radical and an initiator radical. In the polymerization using menthol and neomenthanethiol, hydrogen transfer from these chiral compounds to the growing radical appeared to take place in a helix-sense-selective manner.
• INDUCTION OF A SINGLE-HANDED HELICAL CONFORMATION THROUGH RADICAL POLYMERIZATION OF OPTICALLY-ACTIVE PHENYL-2-PYRIDYL-O-TOLYLMETHYL METHACRYLATE

  Y OKAMOTO, M NISHIKAWA, T NAKANO, E YASHIMA, K HATADA

  MACROMOLECULES 28 14 5135 - 5138 1995年07月 [査読有り][通常論文]
   

  Optically active phenyl-2-pyridyl-o-tolylmethyl methacrylate (PPyoTMA) having Various enantiomeric excesses was polymerized with diisopropyl peroxydicarbonate in toluene at 40 degrees C. Isotactic polymers were obtained. The polymers showed large optical rotations which are opposite in sign to the rotation of the starting monomer and the optical activity was higher than expected from the enantiomeric purity of the monomeric units in the polymer, indicating that a right- or left-handed helix was formed in excess from the steric effect of the chiral side group. Copolymerization of PPyoTMA with triphenylmethyl methacrylate (TrMA) also gave optically active, isotactic polymers; the phenyl-2-pyridyl-o-tolylmethyl group is also effective in inducing an excess of a single-handed helix consisting of TrMA monomeric sequences. Copolymerization with MMA gave atactic polymers showing much smaller optical activity than that of the copolymers with TrMA.
• TOWARD CONTROL OF STEREOCHEMISTRY IN GTP BY A RATIONAL MONOMER DESIGN - CYCLOPOLYMERIZATION OF 2,2'-BIS((METHACRYLOYLOXY)METHYL)-1,1'-BINAPHTHYL

  T NAKANO, DY SOGAH

  JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 117 1 534 - 535 1995年01月 [査読有り][通常論文]
  
• CHIROPTICAL PROPERTIES OF OLIGOMERS OF M-METHYLPHENYL ISOCYANATE BEARING AN OPTICALLY-ACTIVE END-GROUP

  K MAEDA, M MATSUDA, T NAKANO, Y OKAMOTO

  POLYMER JOURNAL 27 2 141 - 146 1995年 [査読有り][通常論文]
   

  Oligomerization of m-methylphenyl isocyanate (mMePI) with lithium amide of (S)-(-)-2-(methoxymethyl)pyrrolidine (MMP) was carried out to obtain oligomers containing a chiral residue at the initial chain end (alpha-end). The oligomers of degree of polymerization (DP) less than eighteen were separated in terms of DP and the specific rotation of each oligomer was estimated. The oligomers showed the high optical rotation which is ascribed to the structure prevailing in one-screw sense. The specific rotation of the oligomers increased up to DP of twelve and then decreased with an increase in DP. This suggests that the DP corresponding to the average persistence length of single handed helix may be larger than twelve. The specific rotation of the polymers was inversely proportional to the molecular weight. The optical activity of the polymer greatly increased with a decrease in temperature, whereas that of the trimer was not influenced by temperature.
• STEREOSPECIFIC AND ASYMMETRIC POLYMERIZATION OF 1-PHENYLDIBENZOSUBERYL METHACRYLATE, WITH RADICAL AND ANIONIC INITIATORS

  Y OKAMOTO, T NAKANO, Y SHIKISAI, M MORI

  MACROMOLECULAR SYMPOSIA 89 479 - 488 1995年01月 [査読有り][通常論文]
   

  Stereospecific and asymmetric (helix-sense-selective) polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) was performed with radical and anionic initiators. A highly isotactic polymer having triad isotacticity greater than 97% was obtained by radical polymerization with (i-PrOCOO)(2) at 40 degrees C. The radical polymerization of PDBSMA in (+)- and (-)-menthol gave (-)- and (+)-polymers, respectively, whose optical activity is ascribed to the prevailing one-handed helical conformation of a polymer chain. The radical copolymerization of PDBSMA with a small amount of an optically active monomer, (+)-phenyl-2-pyridyl-o-tolylmethyl methacrylate, afforded an optically active copolymer with the prevailing one-handed helical structure of PDBSMA sequences. Asymmetric anionic polymerization of PDBSMA was carried out with the complex of N, N'-diphenylethylenediamine monolithium amide and a chiral ligand, (+)-1-(2-pyrrolidinylmethyl)pyrrolidine in toluene at -78 degrees C. The obtained polymer was highly isotactic and optically active due to nearly 100% one-handed helical structure.
• Toward stereochemical control in silicon-mediated polymerizations

  Sogah, Dotsevi Y, Shen, Jianzhong, Nakano, Tamaki

  Book of Abstracts, 210th ACS National Meeting, Chicago 1995年 [査読有り][通常論文]
  
• ASYMMETRIC POLYMERIZATION OF TRIPHENYLMETHYL METHACRYLATE USING 9-ALKYL-9-FLUORENYLLITHIUM-(-)-SPARTEINE COMPLEXES - INFLUENCE OF ORGANOLITHIUM STRUCTURE ON THE PROPAGATION STEREOCHEMISTRY

  T NAKANO, Y OKAMOTO, K HATADA

  POLYMER JOURNAL 27 9 892 - 903 1995年 [査読無し][通常論文]
   

  Asymmetric anionic polymerization and oligomerization of triphenylmethyl methacrylate (TrMA) were carried out with the complexes of (-)-sparteine (Sp) with 9-methyl-9-fluorenyllithium (MeFlLi) and 9-ethyl-9-fluorenyllithium in toluene at -78 degrees C in conjunction with the polymerization of TrMA with Sp-9-fluorenyllithium (FlLi) complex. As well as Sp-FlLi complex, Sp-MeFlLi complex gave an optically active ([alpha](D) +360 degrees), highly isotactic polymer with one-handed helical conformation; the polymer had a higher molecular weight than that obtained by Sp-FILi under the same reaction conditions. The oligomers obtained at the feed ratio of monomer to initiator of two, three, and five were converted to oligo(methyl methacrylate) [oligo(MMA)]; the oligo(MMA)s were first separated in terms of degree of polymerization and then into diastereomers. The dimer meso (m) and raceme (r) and the trimer mm and mr were resolved into enantiomers to determine the ratio of isomers for each oligomer. On the basis of the change in isomer content of the dimer with the change in the feed ratio of monomer to initiator, it was concluded that the dimer anion having S absolute configuration is more active toward TrMA monomer than that having R configuration in both the systems with MeFlLi and EtFlLi in contrast to the reaction with Sp-FlLi where the R-dimer anion is more active. The stereochemistry in the propagation of a trimer anion to a tetramer anion and thereafter appeared similar to the reaction system with Sp-FlLi where -RRR- isomers predominantly propagate, The predominant propagation of the S-dimer anion results in a larger amount of the isomeric anions which do not propagate to the optically active polymer.
• TERMINATION STEREOCHEMISTRY IN ASYMMETRIC ANIONIC-POLYMERIZATION OF TRIPHENYLMETHYL METHACRYLATE - METHYLATION AND PROTONATION OF OLIGOMER ANIONS

  T NAKANO, Y OKAMOTO, K HATADA

  POLYMER JOURNAL 27 9 882 - 891 1995年 [査読無し][通常論文]
   

  Oligomerization of triphenylmethyl methacrylate (TrMA) was carried out with the complex of 9-fluorenyllithium and (-)-sparteine in toluene at -78 degrees C. The reaction was terminated by methylation using methyl iodide and methyl iodide-d(3) or by protonation using methanol, butanol, 2-propanol, and t-butanol. The resulting oligomers were converted to oligo(methyl methacrylate) [oligo(MMA)]; the oligomers were first separated in terms of degree of polymerization and then into diastereomers. The individual diastereomers were resolved into enantiomers and the ratio of isomers was determined for each oligomer. Methylation with methyl iodide-d(3) of dimer anion occurred stereoselectively. Protonation stereochemistry was strongly affected by stereostructure of the protonating alcohols. The effect of alcohol was more obvious for the anions which were less active toward TrMA monomer.
• ASYMMETRIC POLYMERIZATION

  Y OKAMOTO, T NAKANO

  CHEMICAL REVIEWS 94 2 349 - 372 1994年03月 [査読有り][通常論文]
  
• ASYMMETRIC POLYMERIZATION OF AROMATIC ISOCYANATES WITH OPTICALLY-ACTIVE ANIONIC INITIATORS

  Y OKAMOTO, M MATSUDA, T NAKANO, E YASHIMA

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 32 2 309 - 315 1994年01月 [査読有り][通常論文]
   

  The asymmetric anionic polymerization of o-, m-, and p-methylphenyl isocyanates, p-methoxyphenyl isocyanate, p-chlorophenyl isocyanate, 2,6- and 3,4-dimethylphenyl isocyanates, and 1-naphthyl isocyanate was carried out using chiral anionic initiators such as the lithium salts of (-)-menthol, (-)-( 2-methoxymethyl) pyrrolidine, and (+)-1-(2-pyrrolidinylmethyl) pyrrolidine. Although o-methylphenyl isocyanate gave an insoluble polymer and 2,6-dimethylphenyl isocyanate afforded no polymer, the other monomers gave soluble polymers, which showed optical activity due to the prevailing helicity of the polymer chain induced by chiral initiator residues attached to the a-end of the polymer chain. The molecular mechanics conformational calculation for a tetramer of m-methylphenyl isocyanate sup ported the helical conformation of the main chain. The optical rotation of the polymers depended significantly on temperature. (C) 1994 John Wiley & Sons, Inc.
• Optically active methacrylic ester polymers

  Okamoto, Yoshio, Nakano, Tamaki

  1994年 [査読有り][通常論文]
  
• Helix-sense-selective polymerization of methacrylate and conformational characteristics of the polymers

  Okamoto, Yoshio, Nakano, Tamaki

  Prog. Pac. Polym. Sci. 3, Proc. Pac. Polym. Conf., 3rd 111 - 122 1994年 [査読有り][通常論文]
  
• Cyclopolymerization of 2,2'-bis(methacryloyloxymethyl)-1,1'-binaphthyl. Comparison of group transfer (GTP), anionic, and free radical polymerizations

  Nakano, Tamaki, Sogah, Dotsevi Y

  Polymer Preprints 35 2 862 - 863 1994年 [査読有り][通常論文]
  
• Helix-sense-selective polymerization of bulky methacrylates with radical and anionic initiators

  Okamoto, Yoshio, Nakano, Tamaki, Shikisai, Yoshifumi, Matsuda, Akihiro

  Polymer Preprints 35 2 591 - 592 1994年 [査読有り][通常論文]
  
• HELIX-SENSE-SELECTIVE POLYMERIZATION OF PHENYL[BIS(2-PYRIDYL)]METHYL METHACRYLATE AND CHIRAL RECOGNITION ABILITY OF THE POLYMER

  CY REN, CF CHEN, F XI, T NAKANO, Y OKAMOTO

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 31 11 2721 - 2728 1993年10月 [査読有り][通常論文]
   

  A novel monomer, phenyl[bis(2-pyridyl)]methyl methacrylate (PB2PyMA), was synthesized. The solvolysis rate of PB2PyMA measured in CDCl3-CD3OD[1/1 (v/v)] by H-1-NMR spectroscopy at 35-degrees-C was much smaller than those of triphenylmethyl methacrylate (TrMA) and diphenyl-2-pyridylmethyl methacrylate (D2PyMA). PB2PyMA was anionically polymerized with the complexes of organolithiums with (-)-sparteine (Sp), (S,S)-(+)-and (R,R)-(-)-2,3-dimethoxy-1,4-bis(dimethylamino) butanes [(+)- and (-)-DDB ], and (S)-(+)-1-(2-pyrrolidinylmethyl) pyrrolidine (PMP) in toluene at low temperature. The polymers obtained with Sp and DDB complexes showed low optical activity. PMP complexes, particularly that with N,N'-diphenylethylenediamine monolithium amide, were effective in synthesizing a polymer of high optical rotation ([alpha]365(25) approximately +1350-degrees) which was comparable to those of poly (TrMA) and poly (D2PyMA) with one-handed helical structure. The optical rotation of poly (PB2PyMA) in a mixture of CHCl3 and 2,2,2-trifluoroethanol (9/1, v/v) slowly decreased with time. Optically active poly (PB2PyMA) coated on macroporous silica gel was able to resolve racemic compounds as a chiral stationary phase for high-performance liquid chromatography. (C) 1993 John Wiley & Sons, Inc.
• SYNTHESIS AND LIQUID CRYSTALLINITY OF STEREOREGULAR POLYMETHACRYLATES WITH MESOGENIC ESTER GROUPS

  T NAKANO, T HASEGAWA, Y OKAMOTO

  MACROMOLECULES 26 20 5494 - 5502 1993年09月 [査読有り][通常論文]
   

  2-[4-(4'-Methoxyphenyl)phenoxy]ethyl, 3-[4-(4'-methoxyphenyl)phenoxy]propyl, 4-[4-(4'-methoxyphenyl)phenoxy]butyl, 5-[4-(4'-methoxyphenyl)phenoxy]pentyl, and 6-[4-(4'-methoxyphenyl)-phenoxy]hexyl methacrylates were synthesized and polymerized. Anionic polymerization of these monomers was carried out with tert-butylmagnesium bromide in toluene, chloroform, and tetrahydrofuran at low temperature, and radical polymerization was conducted with alpha,alpha'-azobis(isobutyronitrile) in toluene at 60-degrees-C. Highly isotactic (mm 90-97%) and syndiotactic (rr 79-86%) polymers were obtained by anionic polymerization in chloroform and tetrahydrofuran, respectively, and polymers rich in syndiotacticity (rr 56-66%) were obtained by radical polymerization. Thermal properties and liquid crystallinities of the polymers depended greatly on both the tacticity of the main chain and the length of the methylene chain (spacer) in the side group. These observations were interpreted in terms of zigzag (alt-trans) and helical conformations of the main chain of syndio- and isotactic polymers, respectively, and the all-trans conformation of the spacer chain.
• 不斉重合触媒 (新しい重合触媒と技術<特集>)

  岡本 佳男, 中野 環

  化学工業 44 7 560 - 566 化学工業社 1993年07月 [査読無し][通常論文]
  
• STEREOSPECIFIC RADICAL POLYMERIZATION OF 1-PHENYLDIBENZOSUBERYL METHACRYLATE AFFORDING A HIGHLY ISOTACTIC POLYMER

  T NAKANO, M MORI, Y OKAMOTO

  MACROMOLECULES 26 4 867 - 868 1993年02月 [査読有り][通常論文]
  
• ASYMMETRIC POLYMERIZATION OF ISOCYANATES WITH OPTICALLY-ACTIVE ANIONIC INITIATORS

  Y OKAMOTO, M MATSUDA, T NAKANO, E YASHIMA

  POLYMER JOURNAL 25 4 391 - 396 1993年 [査読有り][通常論文]
   

  Anionic polymerization of 3-phenylpropyl, 4-phenylbutyl, and butyl isocyanates was carried out with chiral anionic initiators such as tert-butyllithium-(-)-sparteine complex (t-BuLi-(-)-Sp), lithium (-)-menthoxide, and (+)-1-(2-pyrrolidinylmethyl)pyrrolidine lithium amide. The t-BuLi-(-)-Sp did not afford optically active polymers. However, the alkoxide and amide gave optically active polymers for 4-phenylbutyl and butyl isocyanates. The optical activities are probably based on the prevailing helicity of the polymer chains induced by chiral initiator residues attaching to an alpha-end group of the polymer chain. The optical rotation of the polymers depended greatly on molecular weight and temperature.
• Catalysts for chiral polymerization

  Okamoto, Yoshio, Nakano, Tamaki

  Kagaku Kogyo 44 7 560 - 566 1993年 [査読有り][通常論文]
  
• Synthesis of helical polymers

  Nakano, Tamaki, Okamoto, Yoshio

  Kagaku, Zokan 123 95 - 100 1993年 [査読有り][通常論文]
  
• Synthesis and stereomutation of optically active polymers with helical conformation

  Nakano, Tamaki, Okamoto, Yoshio

  Kikan Kagaku Sosetsu 18 129 - 136 1993年 [査読有り][通常論文]
  
• Studies on synthesis, structure, and application of optically active polymers with helical conformation

  Okamoto, Yoshio, Nakano, Tamaki

  Asahi Garasu Zaidan Josei Kenkyu Seika Hokoku 17 - 24 1993年 [査読有り][通常論文]
  
• ASYMMETRIC POLYMERIZATION OF TRIPHENYLMETHYL METHACRYLATE LEADING TO A ONE-HANDED HELICAL POLYMER - MECHANISM OF POLYMERIZATION

  T NAKANO, Y OKAMOTO, K HATADA

  JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 114 4 1318 - 1329 1992年02月 [査読有り][通常論文]
   

  Asymmetric oligomerization of triphenylmethyl methacrylate (TrMA) was carried out with complexes of 9-fluorenyllithium and chiral ligands in toluene at -78-degrees-C, and the oligomers obtained were converted into methyl esters. The resulting oligo(methyl methacrylate)s were first fractionated by gel permeation chromatography in terms of degree of polymerization and further separated into diastereomers and optical isomers by high-performance liquid chromatography. The distribution of oligomers and the ratio of isomers in each oligomer gave important information on the mechanism of the asymmetric (helix sense selective) polymerization of TrMA. The reactivity of each oligomer anion depended greatly on its degree of polymerization and stereostructure. The oligomer anions whose asymmetric centers have R configuration in the system with the complex of 9-fluorenyllithium and (-)-sparteine and those of S configuration in the systems with (+)-(2S,3S)-2,3-dimethoxy-1,4-bis(dimethylamino)butane and (+)-(S)-1-(2-pyrrolidinylmethyl)pyrrolidine as chiral ligands predominantly propagated to a one-handed helical polymer. A stable helix starts at degree of polymerization 9 in the former system and at degree of polymerization 7 in the latter two systems. One helix turn seems to consist of three or four monomeric units. The main chain of the resulting polymer in the former system possessed RPR--- absolute configuration and that in the latter systems SSS---, though both polymers are considered to be of the same helicity, P or M. These results indicate that the helicity of the polymer is not governed by the configuration of the main chain but by the chirality of the ligands.
• ASYMMETRIC POLYMERIZATION OF CYCLOPROPYLDIPHENYLMETHYL AND CYCLOHEXYLDIPHENYLMETHYL METHACRYLATES AND STEREOMUTATION OF THE POLYMERS

  Y OKAMOTO, T NAKANO, T FUKUOKA, K HATADA

  POLYMER BULLETIN 26 3 259 - 264 1991年08月 [査読有り][通常論文]
   

  Cyclopropyldiphenylmethyl and cyclohexyldiphenylmethyl methacrylates were polymerized with chiral anionic initiators in toluene at low temperature. The former monomer gave an atactic polymer and the latter monomer a highly isotactic, optically active polymer of one-handed helical conformation. The optically active polymer underwent a helix-helix transition in chloroform at 60-degrees-C.
• SYNTHESIS AND REVERSIBLE STEREOMUTATION OF OPTICALLY-ACTIVE POLY((S)-DIPHENYL(1-METHYLPYRROLIDIN-2-YL)METHYL METHACRYLATE)

  Y OKAMOTO, T NAKANO, E ONO, K HATADA

  CHEMISTRY LETTERS 3 525 - 528 1991年03月 [査読有り][通常論文]
   

  Anionic polymerization of (+)-(S)-diphenyl(1-methyl-pyrrolidin-2-yl)methyl methacrylate gave an optically active polymer of helical conformation of single screwsense. The polymer exhibited a reversible helix-helix transition in a solution of methanol containing an acid.
• ASYMMETRIC POLYMERIZATION OF OPTICALLY-ACTIVE PHENYL-2-PYRIDYL-M-TOLYLMETHYL METHACRYLATE AND STEREOMUTATION OF THE POLYMER

  Y OKAMOTO, T NAKANO, T ASAKURA, H MOHRI, K HATADA

  JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 29 2 287 - 289 1991年02月 [査読有り][通常論文]
  
• Synthesis and conformational change of helical polymethacrylates

  Okamoto, Yoshio, Nakano, Tamaki, Hatada, Koichi

  Polymer Preprints 32 1 451 - 452 1991年 [査読有り][通常論文]
  
• HELIX-SENSE-SELECTIVE POLYMERIZATION OF DIPHENYL-2-PYRIDYLMETHYL METHACRYLATE WITH CHIRAL ANIONIC INITIATORS

  Y OKAMOTO, H MOHRI, T NAKANO, K HATADA

  CHIRALITY 3 4 277 - 284 1991年 [査読有り][通常論文]
   

  Polymerization of diphenyl-2-pyridylmethyl methacrylate was carried out with the complexes of organolithium compounds with 22 chiral ligands. Helix-sense-selectivity of the polymerization was largely affected by a slight structural difference of chiral ligands. (+)-(S)-2-(1-Pyrrolidinylmethyl)pyrrolidine was the most effective ligand in producing a one-handed helical polymer with narrow molecular weight distribution.
• STEREOMUTATION OF OPTICALLY-ACTIVE POLY(DIPHENYL-2-PYRIDYLMETHYL METHACRYLATE)

  Y OKAMOTO, H MOHRI, T NAKANO, K HATADA

  JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 111 15 5952 - 5954 1989年07月 [査読有り][通常論文]
  
• OPTICAL-ACTIVITY OF ISOTACTIC OLIGOMERS OF METHYL-METHACRYLATE

  Y OKAMOTO, T NAKANO, K HATADA

  POLYMER JOURNAL 21 2 199 - 201 1989年 [査読有り][通常論文]
  
• Haloaldehyde polymers. XXXV. Proton, fluorine-19, and carbon-13 NMR spectra and stereochemistry of bornyl esters of fluorochlorobromoacetic acid

  Haloaldehyde polymers, XXXV, Proton, fluorine, and carbon, NMR spectra, stereochemistry of bornyl, esters of fluorochlorobromoacetic acid

  Polymer Journal 21 2 171 - 177 1989年 [査読有り][通常論文]
  
• Haloaldehyde polymers. 34. Proton and carbon-13 NMR spectra of chloral oligomers prepared by lithium tert-butoxide initiation and the assignment of the meso/racemo addition products of the dimers

  Hatada, Koichi, Ute, Koichi, Nakano, Tamaki, Vass, Frantisek, Vogl, Otto

  Makromolekulare Chemie 190 9 2217 - 2228 1989年 [査読有り][通常論文]
  
• Synthesis and utilization of helical, optically active polymers

  Okamoto, Yoshio, Nakano, Tamaki

  Yuki Gosei Kagaku Kyokaishi 47 11 1029 - 1039 1989年 [査読有り][通常論文]
  
• CRYSTAL-STRUCTURE OF METHYL-METHACRYLATE DIMER - REVISED MESO/RACEMO ASSIGNMENT FOR THE DIMER

  T NAKANO, K UTE, Y OKAMOTO, Y MATSUURA, K HATADA

  POLYMER JOURNAL 21 11 935 - 939 1989年 [査読有り][通常論文]
  
• Synthesis and reversible helix-helix transition of poly[(S)-diphenyl(1-methylpyrrolidin-2-yl)methyl methacrylate]

  Okamoto, Yoshio, Nakano, Tamaki, Mohri, Haruhiko, Ono, Etsuko, Hatada, Koichi

  Polymer Preprints 30 2 408 - 409 1989年 [査読有り][通常論文]
  
• Asymmetric polymerization of methacrylates leading to a one-handed helix

  Okamoto, Yoshio, Nakano, Tamaki, Mohri, Haruhiko, Asakura, Toshikage, Hatada, Koichi

  Polymer Preprints 30 2 437 - 438 1989年 [査読有り][通常論文]
  
• MECHANISM OF ASYMMETRIC POLYMERIZATION OF TRIPHENYLMETHYL METHACRYLATE - SEPARATION AND OPTICAL RESOLUTION OF OLIGOMERS

  Y OKAMOTO, E YASHIMA, T NAKANO, K HATADA

  CHEMISTRY LETTERS 5 759 - 762 1987年 [査読有り][通常論文]
  

MISC

• 光のキラリティーを用いた高分子らせんの構築 (特集 進化するキラル化学のイノベーション)

  中野 環 化學工業 66 (2) 92 -96 2015年02月 [査読無し][通常論文]
  
• 光による高分子の構造制御

  中野 環 石油学会 年会・秋季大会講演要旨集 2014 (0) 2014年 [査読無し][通常論文]
   

  円偏光をキラル源として高分子・低分子のキラル構造を制御する手法を見出した。この方法により、まず、主鎖共役型高分子に一方向に偏ったらせん構造を誘起することに成功した。さらに、ビニル型高分子および関連する低分子化合物に対しても本手法を適用して光学活性材料を調製した。
• 有機透明導電体を目指すπスタック型高分子の研究

  中野環 ポリマーフロンティア21講演要旨集 2012 (6) 13 -17 2013年03月08日 [査読無し][通常論文]
  
• キラリティと高分子 光でらせんを作る

  中野環 高分子 61 (10) 767 -768 2012年10月01日 [査読無し][通常論文]
  
• ハイパーブランチ光学活性ポリフルオレン誘導体の合成と構造

  渡辺顕士, 鈴木望, 藤木道也, 中野環 高分子学会予稿集(CD-ROM) 61 (2) ROMBUNNO.1E07 2012年09月05日 [査読無し][通常論文]
  
• ビナフチル基を有するキラルな環状オリゴマーの合成と超分子液晶形成

  関口康行, 中野環, 菊池悠嗣, 氏家誠司, 長谷川仁子, 七分勇勝, 小西克明 高分子学会予稿集(CD-ROM) 61 (1) ROMBUNNO.1PG027 2012年05月15日 [査読無し][通常論文]
  
• 光学活性枝分かれポリフルオレン誘導体の合成

  渡辺顕士, 鈴木望, 藤木道也, 中野環 高分子学会予稿集(CD-ROM) 61 (1) ROMBUNNO.3F02 2012年05月15日 [査読無し][通常論文]
  
• かさ高いスチレン誘導体の不斉重合

  村木峻, 渡辺顕士, LI Geng, 中野環 高分子学会予稿集(CD-ROM) 61 (1) ROMBUNNO.2PB012 2012年05月15日 [査読無し][通常論文]
  
• Stereocontrolled Chiral Polymers

  T. Nakano, Y. Okamoto Polymer Science: A Comprehensive Reference, 10 Volume Set 6 629 -687 2012年 [査読無し][通常論文]
   

  Synthesis and structure of conformationally and configurationally chiral polymers are overviewed. Helix is the most representative chiral conformation, and helical polymers can be divided into three types, namely, those with static helix, those with dynamic helix, and those formed by chain folding (foldamers). Single-handed helicity is realized by helix-sense-selective polymerization for polymers with static helix and by covalent or supramolecular interaction of the polymer chain with chiral groups or chiral added molecules for polymers with dynamic helix and for foldamers. Polymers having configurational chirality in the main chain or the side chain are prepared by asymmetric synthesis polymerization or enantiomer-selective polymerization. © 2012 Elsevier B.V. All rights reserved.
• 有機・高分子 π-スタック型高分子の合成と光電子機能

  中野 環 未来材料 10 (10) 25 -31 2010年10月 [査読無し][通常論文]
  
• π-スタック型ポリマー

  中野 環 高分子 59 (3) 164 -168 2010年03月01日 [査読無し][通常論文]
  
• 新規πスタック型高分子の創製と特性解析

  永 直文, 中野 環 特別教育・研究報告集 2007 103 -106 2007年 [査読無し][通常論文]
  
• 2,7-ジペンチルジベンゾフルベンの不斉アニオン重合 (特集号=キラル高分子・超分子(2))

  中野 環, 八重樫 敬之, 中川 修 高分子論文集 63 (7) 492 -497 2006年 [査読無し][通常論文]
  
• π-スタックポリマーの合成と機能 (特集/新たな可能性を拓く先端材料)

  中野 環 化学工業 56 (3) 195 -202 2005年03月 [査読無し][通常論文]
  
• 新しいアニオン重合開始剤系の開発:使い勝手の良い精密重合法を目指して

  中野 環, 矢出 亨, 中川 修 接着 48 (8) 352 -359 2004年08月 [査読無し][通常論文]
  
• 不斉ラジカル重合

  中野 環 高分子論文集 58 (8) 411 -426 2001年 [査読無し][通常論文]
   

  Methods of chiral induction were found for radical polymerization of 1-phenyldibenzosuberyl methacrylate (PDBSMA) and for those of N-phenyl- and N-cyclohexylmaleimide (PMI and CHMI). PDBSMA gives an almost completely isotactic polymer by conventional radical polymerization the product is an equimolar mixture of right- and left-handed helices. Helix-sense selection during the radical polymerization of PDBSMA was realized using optically active peroxides as initiators, thiols as chain-transfer agents (CTA), alcohols as solvents, and cobalt (II) complexes as additives. When the first three chiral sources were used, helix-sense selection took place through termination reactions, i.e. primary radical termination or hydrogen transfer from CTA or solvent to the growing radical. Though the chiral induction mechanism of cobalt (II) is not completely clear, the complex seems to interact with the growing radical. Polymers of PMI and CHMI may contain achiral cis- and chiral trans-monomeric units in the main-chain. Polymerization of the two monomers in the presence of an optically active cobalt (II) complex led to optically active polymers. Through an interaction between the cobalt (II) species and growing radical, either (R,R)- or (S,S)- form of the trans-unit may have been produced in excess.
• Asymmetric polymerization of methacrylates

  T Nakano, Y Okamoto MACROMOLECULAR RAPID COMMUNICATIONS 21 (10) 603 -612 2000年07月 [査読無し][通常論文]
   

  The syntheses of optically active polymers having helical conformation from bulky methacrylates are reviewed focusing on selected topics. The monomers include triphenylmethyl methacrylate and its analogues. Asymmetric anionic polymerization of the monomers gives isotactic, optically active polymers having a helical structure with excess helicity, The isotactic content and the extent of helical-sense excess depend on the monomer structure and the reaction conditions. In the case of methacrylates, completely isotactic and single-handed helical polymers can be produced by asymmetric anionic polymerization (helix-sense-selective polymerization). Asymmetric radical polymerization is also possible for this class of monomer. Some of the helical polymers show chiral recognition ability coward a wide range of racemic compounds. Polymers having main-chain configurational chirality are also discussed.
• Stereospecific radical polymerization of fluoroalkyl acrylates

  WH Liu, T Nakano, Y Okamoto JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 (6) 1024 -1032 2000年03月 [査読無し][通常論文]
   

  The free-radical polymerization of 2,2,2-trifluoroethyl acrylate (TFEA), 1,1,1,3,3,3-hexafluoro-2-propyl acrylate (HFiPA) and perfluoro-tert-butyl acrylate (PFtBA) was carried out under various conditions and the stereostructure of the obtained polymers was investigated. Most polymerizations of the three monomers afforded polymers rich in diad syndiotacticity (r) in bulk or in solution; the r-specificity was higher in the HFiPA and PFtBA polymerization than in the TFEA polymerization. Although the tacticity was nearly independent of reaction temperature during the polymerization of TFEA, the r-specificity increased by lowering the reaction tempera -ture during the polymerization of the other two monomers. The polymerization stereochemistry was also affected by the reaction solvents including toluene, tetrahydrofuran, and fluoroalcohols. It was noted that the stereochemistry of the polymerization of HFiPA and PFtBA also depended on the monomer concentration, and a lower monomer concentration led to a higher r-specificity. By optimizing the aforementioned reaction conditions, the poly(HFiPA) having r = 81% (polymerization in tetrahydrofuran at -98 degrees C at [M](o) = 0.2M) and the poly(PFtBA) having r = 77% (polymerization in toluene at -78 degrees C at [M](o) = 0.2M) were obtained. (C) 2000 John Wiley & Sons, Inc.
• Free-radical copolymerization of vinyl esters using fluoroalcohols as solvents: The solvent effect on the monomer reactivity ratio

  K Yamada, T Nakano, Y Okamoto JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 38 (1) 220 -228 2000年01月 [査読無し][通常論文]
   

  Free-radical copolymerizations of vinyl acetate (VAc = M-1) and other vinyl esters (= M-2) including vinyl pivalate (VPi), vinyl 2,2-bis(trifluoromethyl)propionate (VF6Pi), and vinyl benzoate (VBz) with fluoroalcohols and tetrahydrofuran (THF) as the solvents were investigated. The fluoroalcohols affected not only the stereochemistry but also the polymerization rate. The polymerization rate was higher in the fluoroalcohols than in THF. The accelerating effect of the fluoroalcohols on the polymerization was probably due to the interaction of the solvents with the ester side groups of the monomers and growing radical species. The difference in the monomer reactivity ratios (r(1), r(2)) in THF and 2,2,2-trifluoroethanol was relatively small for all reaction conditions and for the monomers tested in this work, whereas r(1) increased in the VAc-VF6Pi copolymerization and r(2) decreased in the VAc-VPi copolymerization when perfluorotert-butyl alcohol was used as the solvent. These results were ascribed to steric and monomer-activating effects due to the hydrogen bonding between the monomers and solvents. (C) 2000 John Wiley & Sons, Inc.
• Free-radical polymerization of vinyl esters using fluoroalcohols as solvents: Effect of monomer structure on stereochemistry

  K Yamada, T Nakano, Y Okamoto JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 37 (14) 2677 -2683 1999年07月 [査読無し][通常論文]
   

  Free-radical polymerization of vinyl esters including vinyl propionate (VPr), vinyl isobutylate (ViBu), vinyl 2,2-dimethylbutylate (VDMB), vinyl 2,2-dimethylvalerate (VDMV), vinyl 2,2-bis(trifluoromethyl)propionate (VF6Pi), and vinyl benzoate (VBz) was carried out using fluoroalcohols as solvents, and the tacticity of the obtained polymers was determined by NMR analysis of the produced poly(vinyl alcohol) (PVA). The polymerization of VPr, ViBu, VDMB, and VDMV, which are bulkier than VAc, in fluoroalcohols afforded polymers rich in heterotacticity (up to mr = 61%) similar to that of vinyl pivalate (VPi) whereas VAc is known to give a syndiotactic polymer under the reaction conditions used here. The polymerization of VF6Pi, which is the bulkiest among the monomers used in this study, gave a polymer rich in syndiotacticity in bulk and in fluoroalcohols regardless of the structure of the solvents. On the other hand, the polymerization of VBz in fluoroalcohols gave olymers with a higher isotacticity (up to mm = 33%) than bulk polymerization. Thus the monomer structure strongly affected the stereochemistry of the free-radical polymerization of vinyl esters in fluoroalcohols. (C) 1999 John Wiley & Sons, Inc.
• Polymerization of optically active 2-fluorophenyl-4-fluorophenyl-2-pyridylmethyl methacrylate with anionic and radical initiators: Stereospecificity and helix-sense selection

  J Wu, T Nakano, Y Okamoto JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 37 (14) 2645 -2648 1999年07月 [査読無し][通常論文]
   

  Almost optically pure (+)- and (-)-2-fluorophenyl-4-fluorophenyl-2-pyridylmethyl methacrylate (2F4F2PyMA) monomers were obtained by HPLC resolution of the racemic monomer and polymerized with the use of anionic and free-radical initiators. Helix-sense selectivity during the polymerization seemed to be governed mainly by the chirality of the monomer itself, and the polymers obtained by using the complex of N,N'-diphenylethylenediamine monolithium amide with(S)-(+)-1-(2-pyrrolidinylmethyl)-pyrrolidine (PMP) in toluene at -78 degrees C appeared to possess single-handed helical conformation (+)-poly[(-)-2F4F2PyMA], [alpha](365) + 1510 degrees; (-)-poly[(+)-2F4F2PyMA], [alpha](365) - 1610 degrees]. The single-handed helical (+)-poly[(-)-2F4F2PyMA] and (-)-poly[(+)-2F4F2PyM] obtained with the PMP complex exhibited better chiral recognition ability toward trans-stilbene oxide compared with the single-handed helical poly(rac-2F4F2PyMA) prepared previously. (C) 1999 John Wiley & Sons, Inc.
• Asymmetric anionic polymerization of (2-fluorophenyl)(4-fluorophenyl)(2-pyridyl) methyl methacrylate leading to a helical polymer

  J Wu, T Nakano, Y Okamoto JOURNAL OF POLYMER SCIENCE PART A-POLYMER CHEMISTRY 36 (12) 2013 -2019 1998年09月 [査読無し][通常論文]
   

  A novel racemic methacrylate, (2-fluorophenyl)( 4-fluorophenyl)( 2-pyridyl)-methyl methacrylate(1) (2F4F2PyMA), was synthesized and polymerized with chiral complexes of N,N'-diphenylethylenediamine monolithium amide (DPEDA-Li) with (-)-sparteine (Sp), (2S, 3S)-(+)-2,3-dimethoxy-1,4-bis(dimethylamino)bu (DDB), and (S)-(+)-1-(2-pyrrolidinylmethyl)pyrrolidine (PMP) in toluene at -78 degrees C. The monomer showed higher resistance against methanolysis compared with triphenylmethyl methacrylate (TrMA) and several other analogues. In the asymmetric anionic polymerization of 2F4F2PyMA, PMP was found to be a more effective chiral ligand than DDB and Sp and gave quantitatively an optically active polymer with nearly perfect isotacticity. Enantiomer selection was observed in the polymerization of racemic 2F4F2PyMA with the chiral lithium complexes. Chiral recognition ability of the optically active poly( 2F4F2PyMA) was examined by an enantioselective adsorption experiment. (C) 1998 John Wiley & Sons, Inc.
• ラジカル重合における立体規制

  中野 環 高分子学会予稿集 46 (1) 64 -66 1997年05月10日 [査読無し][通常論文]
  
• ラジカル重合による立体制御と不斉誘導

  中野 環 高分子 46 (2) 81 -81 1997年02月 [査読無し][通常論文]
  
• 剛直ならせん状高分子を鋳型に用いる液晶性分子の配列制御

  中野 環 日産科学振興財団研究報告書 (20) 139 -142 1997年 [査読無し][通常論文]
  
• "Towards control of stereochemistry and chirality in methacrylate polymers."

  Dotsevi Y. Sogah, S. Zheng, T. Nakano American Chemical Society, Polymer Preprints, Division of Polymer Chemistry 37 442 -443 1996年08月01日 [査読無し][通常論文]
  
• Asymmetric anionic polymerization of 1-phenyldibenzosuberyl and 1-(2-pyridyl)dibenzosuberyl methacrylates and chiral recognition ability of the obtained polymers

  T Nakano, A Matsuda, M Mori, Y Okamoto POLYMER JOURNAL 28 (4) 330 -336 1996年 [査読無し][通常論文]
   

  Asymmetric anionic polymerization of 1-phenyldibenzosuberyl methacrylate [5-phenyldibenzosuberan-5-yl methacrylate, 5-phenyl-10,11-dihydrodibenzo[a,d]cyclohepten-5-yl methacrylate] (1), and 1-(2-pyridyl)dibenzosuberyl methacrylate] [5-(2-pyridyl)dibenzosuberan-5-yl methacrylate, 5-(2-pyridyl)-10,11-dihydrodibenzo[a,d]cyclohepten-5-yl methacrylate] (2) was carried out using complexes of N,N'-diphenylethylenediamine monolithium amide with (-)-sparteine (Sp), (+)-1-(2-pyrrolidinylmethyl)pyrrolidine (PMP), and (+)-2,3-dimethoxy-1,4-bis(dimethylamino)butane (DDB) in toluene at -78 degrees C. The polymers of 1 quantitatively obtained with the three complexes were highly isotactic and showed high optical activity ([alpha](365) + 1670-1780 degrees, [alpha](D) + 420-480 degrees) and intense circular dichroism absorptions based on one-handed helical conformation of main chain. In contrast, 2 gave one-handed helical polymers only by the polymerization with the Sp and PMP complexes. The polymerization of 2 with the DDB complex was sluggish. Monomers 1 and 2 showed higher resistance against methanolysis compared with triphenylmethyl methacrylate and diphenyl-2-pyridylmethyl methacrylate, respectively. The obtained optically active polymers resolved several racemic compounds.
• 新しい高分子--らせん構造を有する光学活性高分子の合成と構造ならびに応用に関する研究

  岡本 佳男, 中野 環 旭硝子財団助成研究成果報告 (1993) 17 -24 1993年11月 [査読無し][通常論文]
  
• 高分子のらせんをつくる (モレキュラ-・キラリティ---高次機能分子の開拓と創薬への展開をめざして) -- (キラル識別,誘導に高分子,複合系を使う)

  中野 環, 岡本 佳男 化学 増刊 (123) 95 -100 1993年05月 [査読無し][通常論文]
  
• ラジカル重合による高度にイソタクチックなポリマーの合成

  中野 環, 岡本 佳男 高分子 42 (11) 923 -923 1993年 [査読無し][通常論文]
  
• らせん構造を有する光学活性ポリマ-の合成とコンホメ-ション変化 (精密重合) -- (立体特異性の制御)

  中野 環, 岡本 佳男 季刊化学総説 (18) 129 -136 1993年 [査読無し][通常論文]
  

書籍等出版物

• Asymmetric Polymerization

  中野 環 (担当:分担執筆範囲:In Encyclopedia of Polymeric Nanomaterials)
  Elsevier 2015年
• π-stacked polymers and molecules : theory, synthesis, and properties

  中野 環 
  Springer 2014年 (ISBN: 9784431541288)
• Synthesis and Properties of pi-Stacked Vinyl Polymers

  中野 環 (担当:分担執筆範囲:In Synthesis and Properties of pi-Stacked Vinyl Polymers)
  Springer Japan 2013年
• pi-Stacked Polymers and Molecules: Theory, Synthesis, and Properties

  中野 環 (担当:編者(編著者))
  Springer Japan 2013年
• Comprehensive Polymer Science 2nd Ed

  Elsevier 2011年
• 新訂 ラジカル重合ハンドブック

  NTS 2010年
• 新規πスタック型ポリマーの合成と光電子機能

  中野 環 
  [奈良先端科学技術大学院大学] 2006年

所属学協会

• バイオインダストリー協会   光化学協会   有機合成化学協会   日本化学会   高分子学会   アメリカ化学会   The American Chemical Society   The Chemical Society of Japan   The Society of Polymer Science, Japan   

共同研究・競争的資金等の研究課題

• 光による高分子の高次構造・物性の制御

  文部科学省：科学研究費補助金(基盤研究(B))

  研究期間 : 2010年 -2012年 

  代表者 : 中野 環

   

  光刺激による高分子のコンホメーション制御と物性制御を実現する目的で、前年度に引き続き、ランダムコイル-ヘリックス転移を実現できる高分子の構造を研究した。代表者らの従来の研究成果から、光照射によるビフェニル基のねじれ-平面転移を起こす構造を主 鎖内に含むポリ(9,9-ジオクチルフルオレン-2,7-ジイル)(PDOF)が円偏光により光学活性化すること見出しており、この現象に関する詳細な知見を得た。まず、円偏光で誘起されたキラル構造の熱および直線偏光にたいする安定性を検討したところ、比較的高い非対称性を示す試料については、光および直線偏光照射によりCDスペクトル強度が大きく減少したが、比較的小さい非対称性を有する試料についてはスペクトル強度は増大した。次に、従来不斉誘起は固体フィルムでのみ可能であったが、溶媒系探索の結果、トルエン-メタノール今後溶媒中に懸濁させた状態でも円偏光による不斉誘起が可能であることを見出した。この成果は円偏光で作ったキラルポリマーを塗布加工できる可能性に繋がるものである。さらに、前年度検討したβ相と不斉誘起の関係についての知見をもとに、β相の割合を大きくした薄膜に円偏光照射することにより、Kuhnの非対称性因子(gCD)が10のマイナス２乗オーダーの高い非対対称性を達成することができた。加えて、本研究で調整した光学活性なPDOFの薄膜が高効率な円偏光発光を示すことを見出した。
• πースタック型導電性ビニルポリマーの合成と機能

  文部科学省：科学研究費補助金(挑戦的萌芽研究)

  研究期間 : 2011年 -2011年 

  代表者 : 中野 環

   

  チオフェン含有πスタック型ポリマーの原料となるモノマーとして4-メチレンシクロペンタ[2,1-b;3,4-b']ジチオフェン(MCPDT)の合成法を確立した。3-ブロモチオフェンとn-BuLiの反応により3-リチオチオフェンを調製し、これをチオフェン-3-カルバルデヒドと反応させてジ(3-チエニル)メタノールを得た。これをヨウ素化してビス(3-(2-ヨウ化チエニル))メタノールとしたのち、PCCでアルコール残基を酸化し、さらに銅触媒により縮環させてシクロペンタ[2,1-b;3,4-b']ジチオフェン-4-オンを合成した。これにMeMgBrを加えて、4-メチルシクロペンタ[2,1-b;3,4-b']ジチオフェン-4-オールとした後にp-TsOHを用いて脱水し、MCPDTを得た。MCPDTをn-BuLiを用いてアニオン重合したところ効率よくポリマーが得られた。また、ラジカル重合でもポリマーが得られた。いずれの重合法で得られたポリマーもπスタック型構造を有することを明らかにした。但し、 研究を通じて、MCPDTモノマーは空気中の酸素と反応してビニル型でない構造を有する高分子を与えることが見出されたため、モノマーの保存・及び重合反応は窒素下で行う必要があることが分かった。アニオン重合およびラジカル重合のいずれでもπスタック型の高分子が得られたが、ラジカル重合体のほうが若干コンホメーション選択性が低いことが示唆された。加えて、ラジカル重合体はアニオン重合体に比べて良好な溶解性を示した。これは、わずかな構造の乱れによって分子鎖聞の相互作用が弱くなったためと推定される。 さらに、新しいπスタック型高分子として側鎖にメトキシエトキシ基を有するポリジベンゾフルベン誘導体の合成に成功した。この高分子は無置換体に比べてはるかに高い溶解性を示した。
• 光でらせんをつくる

  文部科学省：科学研究費補助金(挑戦的萌芽研究)

  研究期間 : 2009年 -2010年 

  代表者 : 中野 環, 坂本 猛

   

  本研究は、従来、触媒的合成反応や超分子的相互作用を用いて制御されてきた高分子の一方向巻きのらせん構造を、光(円偏光)のみを用いて制御することを目的とした。代表者らの従来の研究成果から、光照射によるビフェニル基のねじれ-平面転移が高分子鎖の構造変化の誘起に有効であることが判明していたため、側鎖にビフェニル残基を有し、光で構造を変えられると考えられるポリ[2,7-ビス(4-t-ブチルフェニル)ジベンゾフルベン](poly-1)を合成した。合成は、光学活性アニオン開始剤およびアキラルなアニオン開始剤を用いて行った。光学活性なメントキシカリウムを用いた重合では一方向に偏ったらせん構造を有すると考えられる光学活性ポリマーが得られた。この光学活性ポリマーに非偏光を照射したところ、ポリマーの円偏光二色性スペクトルには顕著な変化が観測され、らせん構造が一部ラセミ化あるいはランダムコイル化したことが示唆された。これにより、poly-1が光で構造を変えるポリマーであることが確認されたため、次に、アキラルなpoly-1に溶液中で円偏光を照射した。しかし、光照射後のポリマーは優位なキラル物性を示さなかった。これは、この物質の溶液中でのKuhn非対称因子が非常に小さいためと考えられた。そこで、次にアキラルなpoly-1を薄膜状にして円偏光を照射したところ、薄膜はキラル物性を示し、光により一方向に偏った...
• 光幾何異性化する新規高分子の創成

  文部科学省：科学研究費補助金(萌芽研究)

  研究期間 : 2006年 -2007年 

  代表者 : 中野 環

   

  最終目的生成物である高分子のモノマー単位のモデルとしての9,9'-ビフルオレニリデンのキラリティーと光異性化について、ポリマーについての検討に先立って、試験的な実験を行った。この目的で、9,9'-ビフルオレニリデンと(+)-ビナフトールを混合してメタノール溶液として、あるいは9,9'-ビフルオレニリデンと(-)-メントールを混合してトルエン溶液として、あるいは9,9'-ビフルオレニリデンと(-)-α-(2,4,5,7-テトラニトロ-9-フルオレニリデンアミノキシ)プオピオン酸を混合してメタノール溶液として、あるいは9,9'-ビフルオレニリデンと(-)-α-(2,4,5,7-テトラニトロ-9-フルオレニリデンアミノキシ)プオピオン酸を混合してメタノール溶液として、窒素雰囲気下で500Wのハロゲン灯を照射した。その結果、前年度(+)-ピネンをキラル源として用いた場合に観測された円偏光二色性(CD)スペクトルはほとんど見られず、(+)-ピネンに比べて、他の3種のキラル化合物は9,9'-ビフルオレニリデンの光異性化においてキラル誘起のためには有効でないことが明らかになった。以上に加えて、9,9'-ビフルオレニリデンと(-)-α-(2,4,5,7-テトラニトロ-9-フルオレニリデンアミノキシ)プオピオン酸の錯体形成による、9,9'-ビフルオレニリデンの光学分割も試みた。両者を混合してメ...
• 新規πスタック型ポリマーの合成と光電子機能

  文部科学省：科学研究費補助金(基盤研究(C))

  研究期間 : 2004年 -2005年 

  代表者 : 中野 環

   

  これまでπ-スタック型ポリジベンゾフルベンの合成には複雑な操作を必要とするアニオン重合法が不可欠であったが、本研究ではほぼ同様の合成を安価で簡便なラジカル重合によって実現した。同時に、ラジカル重合体には極僅かな構造欠陥が含まれるが、これが高分子の溶解性の向上に大きく貢献することも見出した。また、かさ高い側鎖基を有する新規なジベンゾフルベンの誘導体として2,7-ジ-t-ブチルジベンゾフルベンを合成し、その重合性と生成物の立体構造および物性について調べた。この化合物の重合反応性は低く、重合生成物はオリゴマーであった。得られたオリゴマーの吸収発光特性から無置換ジベンゾフルベンの特異的な光物理化学的性質発現の機構についての知見が得られた。さらに、ジベンゾフルベンオリゴマーおよびポリマーの化学酸化によりラジカルカチオンを発生させ、その分光学的分析を行った。ラジカルカチオン種は近赤外領域に明確な電荷移動吸収体を示し、πススタック構造を通じて電荷の非局在化が起こり得ることを示した。加えて、ポリジベンゾフルベン型ポリマー以外の汎用的なビニルポリマーに対してπ-スタック構造を実現することを目的として、種々のタクチシチーを有するポリ(メタクリル酸フルオレニル)を立体特異性アニオン重合法により合成し、生成ポリマーの立体構造と性質を調べた。得られたポリマーは安定なπ-スタック構造を保持できないことが...
• 分子インプリント法によるレドックス活性高分子ゲルの合成と分子認識への応用

  文部科学省：科学研究費補助金(特定領域研究(B), 特定領域研究)

  研究期間 : 2001年 -2003年 

  代表者 : 幅上 茂樹, 山本 智代, 中野 環, 覚知 豊次, 波多野 豊平

   

  一方向巻きのらせん構造を有するポリ(メタクリル酸エステル)誘導体をテンプレートとして用い,分子インプリント法を応用することにより,キラルならせん状空孔の形成,さらには,多様なキラル分子に対する不斉認識能を有する新規高分子ゲルの構築について検討した.これまでの研究より,共重合モノマーとしてα-(ベンジルオキシメチル)アクリル酸誘導体を用いることにより,通常分子インプリント法で用いられるメタクリル酸などに比べ,.より効果的にキラルゲルを構築できることを明らかにしている.これはテンプレートと2点で相互作用することが可能なこの2官能性モノマーの特徴的な構造に基づくものであると考えられる.そこで,実用性の観点から,市販の種々の2官能性モノマーを共重合モノマーとして用いた新規キラルゲル構築法について検討した.2官能性モノマーとしてマレイン酸誘導体などを用い,これまでに確立した方法を応用し,キラルゲルの構築を行った.その結果,いずれの場合にもほぼ定量的にゲルを合成することができた.得られたゲルの不斉認識能をtrans-スチルベンオキシド,トレガー塩基などのラセミ体を用いて不斉吸着実験による評価を行った.その結果,いずれのゲルも不斉識別能を示した.たとえばマレイン酸から得られたゲルは,特にtrans-スチルベンオキシドに対して高い不斉識別能を示し,市販の2官能性モノマーを用いた本手法が,有効...
• 遷移金属錯体を用いたラジカル重合の立体制御に関する研究

  文部科学省：科学研究費補助金(奨励研究(A))

  研究期間 : 1999年 -2000年 

  代表者 : 中野 環

   

  重合系の成長ラジカルと相互作用し得る光学活性金属ラジカル種を設計、合成し、ラジカル重合系に添加して生成ポリマーの立体構造に与える影響について調べた。金属ラジカル種としては光学活性な(R,R)-N,N-ビス(3,5-tert-ブチルサリチリデン)-1,2-シクロヘキサンジアミナトコバルト(II)および銅(II)を用い、トルエン-ピリジン(95/5)中あるいはテトラヒドロフラン-THF中でα,α'-アゾビスイソブチロニトリルを開始剤とするN-シクロへキシルマレイミド(cHMI)のラジカル重合について検討した。コバルト錯体存在化で生成したポリマーには主鎖の不斉炭素の絶対配置の偏りに基づくと考えられる旋光性および円偏光二色性スペクトルが観測された。光学活性コバルト錯体の影響でラジカル重合中に主鎖に不斉誘導がおきたことが示唆された。この重合反応は、コバルト錯体存在下ではラジカル禁止剤であるTEMPOを加えても進行し、また、モノマーとコバルト錯体の溶液を室温に放置するだけでも効率良く進行した。この事から、重合機構にはフリーラジカル重合種は含まれておらず、また、モノマーとコバルト錯体の相互作用により活性種が発生することが示唆された。銅錯体はコバルト錯体ほどの不斉誘導効果は示さなかった。
• 高性能キラル分離剤の開発と分離機構の解明

  文部科学省：科学研究費補助金(基盤研究(A))

  研究期間 : 1996年 -1998年 

  代表者 : 岡本 佳男, 幅上 茂樹, 市田 昭人, 中野 環, 八島 栄次

   

  1. グルコース1-リン酸を酵素ホスホリラーゼを用いて酵素重合することにより、アミロースの還元末端部位をただ一点でシリカゲルに化学結合させることができ、フェニルイソシアナートを反応させることで、一点化学結合型キラル固定相を調製した。またこれを高速液体クロマトグラフィー(HPLC)用のキラル固定相に用いその光学分割能を評価したところ、従来の担持型カラムと同等の高い分割能が得られ、また担持型では使用できない多糖誘導体を溶かす溶媒を溶離液に用いることができ、耐久性を兼ね備えた実用的なキラル固定相となることが明らかになった。さらに、酵素重合法により得られた、分子量分布の狭く重合度が100以下のアミロースを用いて3,5-ジメチルフェニルカルバメート誘導体(AD)を合成したところ、得られたADはクロロホルムに可溶であり、NMRとHPLCを用いてその不斉識別機構の解明を議論することが可能になった。ADは多糖誘導体の中でも最も高い光学分割能を有する誘導体の一つであり、その機構の解明は、大変意義深いものである。また、ADの二次元NOESYスペクトルを測定することにより、その構造解析を行い、分子モデリングを行うことでそのモデルの構築に成功した。2. 酵素重合法で得られたアミロース、及びそのオリゴマー等を、超微量分析の可能なキャピラリー電気泳動用のキラル添加剤に用い、医薬品を含む様々なラセミ体の光...
• 鋳型錯体の形成を利用したラジカル重合の立体制御

  文部科学省：科学研究費補助金(萌芽的研究)

  研究期間 : 1996年 -1997年 

  代表者 : 中野 環

   

  ビニルモノマーのラジカル重合の立体規制を目的として、まず、粘土(モンモリロナイト、サポナイト)と2-および4-ビニルピリジンの塩酸塩の錯体を形成させ、粘土の層間での重合を試みた。モンモリロナイト、サポナイトいずれを用いた場合にもモノマーの塩酸塩は効率よく粘土中に取り込まれた。錯体に紫外線照射して重合を試みたところ、2-5量体程度のオリゴマーが主に生成し高分子量の生成物は得られなかった。次に粘土に換えて、臭化マグネシウム、臭化リチウム、光学活性なメントキシマグネシウムブロミド、メントキシリチウムの存在下での2-および4-ビニルピリジンおよびメタクリル酸2-ピリジルメチルの重合について検討した。2-ビニルピリジンの重合の立体化学には金属塩の影響はほとんど見られなかったが、4-ビニルピリジンの場合には金属塩の存在により生成ポリマーのイソタクチック含量が増加する傾向が明確に見られた。これはモノマーおよび成長種のピリジル基に金属塩が配位した結果、モノマーおよび成長種が見掛け上嵩高くなったためと考えられる。ただし、光学活性錯体を用いても有意な不斉誘起は確認されなかった。メタクリル酸2-ピリジルメチルの重合でもリチウム塩、マグネシウム塩との錯体形成による重合の立体化学への影響が見られ、金属塩の存在によりイソタクチック選択性が向上し、シンジオタクチック選択性が低下する現象が観測された。
• ラジカル重合による立体制御に関する研究

  文部科学省：科学研究費補助金(一般研究(B), 基盤研究(B))

  研究期間 : 1995年 -1996年 

  代表者 : 岡本 佳男, 幅上 茂樹, 中野 環, 八島 栄次

   

  反応の立体制御を目的として、(R,R)-N,N′-ビス(3,5-ジ-t-ブチルサリチリデン)-1,2-シクロヘキサンジアミナトコバルト(II)(1)を含む様々なコバルト錯体存在下でのビニルモノマーのラジカル重合を行った。メタクリル酸トリフェニルメチルの重合の立体化学は、コバルト錯体の存在に強く影響され、特に1は三連子イソタクチシチ-を約20%程度減少させ、同時に生成物の分子量分布を狭くする(Mw/Mn1.2-1.5程度)効果をもつことが明らかになった。また、種々のソルビン酸エステルの、コバルト錯体を用いない通常のラジカル重合では、比較的高分子量(Mn13万程度)の1,4-トランス重合体と併せて比較的低分子量(Mn3千程度)の未反応ビニル基を持つポリマーが副成することを見いだし、1を重合系に添加することにより低分子量ポリマーの生成を抑制することに成功した。さらに、通常のラジカル重合でほぼ完全にイソタクチックでらせん構造を持つポリマー(左右のらせんの等量混合物)を与えるメタクリル酸1-フェニルジベンゾスベリルを、光学活性な1の存在下で重合したところ生成ポリマーのらせんの向きが制御され、完全に一方向巻きのらせん構造をもつ光学活性ポリマーが得られた。また、錯体1はスチレン、酢酸ビニルの重合制御にも有効で、リビング的な成長を実現し、生成物の立体構造には錯体の影響が僅かだが見られた。これ...
• 実用的光学分割システムの開発

  文部科学省：科学研究費補助金(試験研究(B))

  研究期間 : 1993年 -1995年 

  代表者 : 岡本 佳男, 中野 環, 市田 昭人, 猪爪 信夫, 八島 栄次, 幅上 茂樹, 中野 環

   

  1.フェニル基上の様々な位置に、メチル基とクロロ基やフルオロ基などのハロゲンを同時に有するセルロースやアミロースの2置換フェニルカルバメート誘導体を合成し、置換基の位置およびその種類の光学分割能におよぼす影響について調べた。セルロース誘導体では、メタおよびパラ位に置換基を有する誘導体が高い分割能を示したのに対し、オルト位に置換基を有する誘導体の分割能は低かった。一方、アミロース誘導体の場合は、セルロース誘導体とは異なり、オルト位に置換基を有する誘導体が、最も高い光学分割能を示した。2.1.で合成した多糖誘導体の幾つかは、クロロホルムなどの極性の低い溶媒に可溶であったので、光学異性体と多糖誘導体とが相互作用している様子をNMRを用いて直接調べることができた。例えば、セルロースの3-フルオロ-5-、メチルフェニルカルバメート誘導体は、1,1'-ビ-2-ナフトールのS体と強く相互作用し、多糖との間で明確なNOE相関ピークが観測された。また、NMRによる滴定実験、緩和時間及びケミカルシフトの変化、コンピュータモデリングをもとに多糖誘導体と1,1'-ビ-2-ナフトールとの錯体のモデルを組立て、不斉識別のメカニズムを分子レベルで解明することができた。また、セルローストリスフェニルカルバメートおよびセルローストリス(3,5-ジメチルフェニルカルバメート)とトランス-スチルベンオキシドとの相...
• らせん構造を有する光学活性高分子の合成、構造、ならびに不斉識別能に関する研究

  文部科学省：科学研究費補助金(一般研究(A))

  研究期間 : 1992年 -1994年 

  代表者 : 岡本 佳男, 中野 環, 八島 栄次, 幅上 茂樹

   

  1.メタクリル酸1-フェニルジベンゾスベリル(1)、メタクリル酸1-(2-ピリジル)ジベンゾスベリル(2)、メタクリル酸フェニル-ビス(2-ピリジル)メチル(3)、およびメタクリル酸ジフェニル-3-ピリジルメチル(4)から(+)-1-(2-ピロジニルメチル)ピロリジン等の錯体を用いたアニオン重合により、一方向巻のらせん構造を有する光学活性ポリマーが得られた。1、2については、光学活性な溶媒中あるいは連鎖移動剤存在下でのラジカル重合でも、らせんの偏りをもつ光学活性ポリマーが得られた。また2-4の光学活性ポリマーはいくつかのラセミ体に対して不斉識別能を示した。芳香族イソシアナ-トを(+)-1-(2-メトキシメチル)ピロリジンのリチウムアミドなど光学活性開始剤を用いて重合することにより、らせんの偏りをもつ光学活性ポリマーが得られた。3.側鎖に光学活性なカルバメート基を有するフェニルアセチレン誘導体から、Rh触媒を用いた重合によって、らせん状光学活性ポリマーを得た。生成ポリマーを高速液体クロマトグラフィー用のキラル固定相として用いたところ、種々のセラミ体を効率良く光学分割することができた。
• 光学活性高分子を用いるキラル分離に関する研究

  文部科学省：科学研究費補助金(重点領域研究)

  研究期間 : 1993年 -1993年 

  代表者 : 岡本 佳男, 中野 環, 八島 栄次

   

  本研究では、高速液体クロマトグラフィー(HPLC)用のキラル充填剤として、すぐれた不斉識別能を有する新規な多糖誘導体の合成を行い、その不斉識別能を評価するとともに、NMRによる不斉識別機構の解明を行った。1.フェニル基上の様々な位置に、メチル基とクロロ基を同時に有する多糖の二置換フェニルカルバメート誘導体を合成した。セルロース誘導体では、メタおよびパラ位に置換基を有する誘導体が極めて高い分割能を示したのに対し、アミロース誘導体では、オルト位に置換基を有する誘導体が最も高い光学分割能を示した。2.側鎖の2、3位および6位を位置特異的にフェニルカルバメートおよびベンゾエート基で修飾した多糖誘導体を合成し、その光学分割能を調べたところ、セルロース誘導体では、側鎖の置換基の位置と種類により光学分割能は変化した。一方、アミロース誘導体では、側鎖を位置特異的に変換した誘導体より、ランダムに変換した誘導体が高い不斉識別能を示し、実用性の高いカラムとなることが明かになった。3.多糖フェニルカルバメート誘導体を少量のジイソシアナートを用いてシリカゲルに位置特異的に化学結合したところ、優れた耐久性と多くのラセミ体に対して、従来の吸着型充填剤と変わらない高い光学分割能を有することが明らかになった。4.セルローストリス(4-トリメチルシリルフェニルカルバメート)(CTMSC)は、高い不斉識別能を示し...
• キラル高分子、光電子機能性高分子

  研究期間 : 1989年
• Chiral polymers, Polymers with photoelectronic properties

  研究期間 : 1989年

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• 特開2012-072352:化合物及び該化合物を含む膜  2012年04月12日

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• 特開2012-046473:有機半導体化合物  2012年03月08日

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• WO2006-109560:光学活性な共重合体、その製造方法及びその共重合体を用いたクロマトグラフィー用充填剤  2006年10月19日

  中野 環, 八重樫 敬之, 辻 雅司  国立大学法人 奈良先端科学技術大学院大学, 独立行政法人科学技術振興機構  200903001854233531
• 特許第3773362号:ラジカル重合における立体規則性の制御方法  2006年02月24日

  山田 和信, 磯部 豊, 岡本 佳男, 中野 環, 澤本 光男, 北畠 千嗣, 寺田 和俊, 井田 大嗣, 岡野 善道, 西村 政通, 加納 芳明, 沖 祥嘉  財団法人化学技術戦略推進機構  200903077097794322
• 特許第3758856号:ヘテロタクチシチーに富むポリビニルアルコールの 製造方法  2006年01月13日

  山田 和信, 岡本 佳男, 中野 環, 澤本 光男, 北畠 千嗣, 寺田 和俊, 井田 大嗣, 加納 芳明, 沖 祥嘉, 岡野 善道, 西村 政通  財団法人化学技術戦略推進機構  200903087895055860
• 特許第3624059号:メタクリル酸又はその誘導体の新規な立体制御重合法  2004年12月03日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903090987454720
• 特開2004-002684:結晶性を有するブロック共重合体および粘着剤  2004年01月08日

  中野 環, 安藤 卓史  ニッタ株式会社  200903056817253777
• WO2003-102039:光学活性な高分子化合物  2003年12月11日

  中野 環  独立行政法人科学技術振興機構  200903055865909572
• WO2003-095523:熱分解性ポリマー  2003年11月20日

  中野 環  独立行政法人科学技術振興機構  200903079798366646
• WO2003-095519:側鎖にπ共役基を有する新規ポリエステル及びこのポリエステルを用いた電荷輸送材料  2003年11月20日

  中野 環  独立行政法人科学技術振興機構  200903081219536114
• WO2002-088202:特異な光特性を有する高分子化合物及びそれに用いる重合性単量体  2002年11月07日

  中野 環  独立行政法人科学技術振興機構  200903056818051779
• 特開2002-146625:ポリビニルアルコール系繊維およびその製造方法  2002年05月22日

  岡本 佳男, 中野 環, 幅上 茂樹, 澤本 光男, 上垣外 正己, 永田 直彦, 長柄 佳孝, 寺田 和俊, 大竹 富明  財団法人 化学技術戦略推進機構  200903064767718687
• 特開2001-200008:シンジオタクチシチーに富むポリビニルアルコールの製造方法  2001年07月24日

  岡本 佳男, 中野 環, 澤本 光男, 上垣外 正己, 永田 直彦, 長柄 佳孝, 山田 和信, 寺田 和俊, 大竹 富明, 金坂 順一郎, 沖 祥嘉, 岡野 善道, 西村 政通  財団法人 化学技術戦略推進機構  200903046761431493
• 特許第3184620号:光学活性なメタクリル酸の重合体  2001年04月27日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903016797617171
• 特開2001-114828:光学活性メタクリル酸エステル重合体及びその製造方法  2001年04月24日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903000441476790
• 特開2001-114832:新規なメタクリル酸エステル及びその製法、並びに新規なポリメタクリル酸エステル及びその製法  2001年04月24日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903018202940287
• 特開2000-128910:光学活性な架橋ゲルの合成法  2000年05月09日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903040299744628
• 特開平11-147916:シンジオタクチシチーに富むポリビニルアルコールの製造方法  1999年06月02日

  山田 和信, 岡本 佳男, 中野 環, 澤本 光男, 中島 宏, 寺田 和俊, 井田 大嗣, 旭 哲也, 沖 祥嘉, 岡野 善道, 西村 政通  財団法人 化学技術戦略推進機構  200903049894117006
• 特開平11-147913:シンジオタクチシチーに富むポリビニルアルコールの 製造方法  1999年06月02日

  山田 和信, 岡本 佳男, 中野 環, 澤本 光男, 中島 宏, 寺田 和俊, 井田 大嗣, 旭 哲也, 沖 祥嘉, 岡野 善道, 西村 政通  財団法人 化学技術戦略推進機構  200903078545190626
• 特開平11-124365:新規なメタクリル酸エステル、その製造法及びその光学分割法、並びに新規なポリメタクリル酸エステル、その製造法及びそれからなる光学分割剤  1999年05月11日

  岡本 佳男, 中野 環, 呉 健  ダイセル化学工業株式会社  200903092251168935
• 特開平11-116627:光学活性メタクリル酸エステル重合体、その製造法及びそれからなる光学分割用分離剤  1999年04月27日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903039674648684
• 特開平9-132610:(メタ)アクリル酸エステルの重合法  1997年05月20日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903046898102942
• 特開平8-208749:光学活性メタクリル酸エステル重合体及び分離剤  1996年08月13日

  岡本 佳男, 中野 環  ダイセル化学工業株式会社  200903018646608947