高分子　Vol.59　No.10

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特集　精密重合の最前線

グローイングポリマー　Growing Polymers: A Personal Account

シクロデキストリンとの日々 Days with Cyclodextrins

奥村　泰志 Yasushi OKUMURA

＜要旨＞ Looking back at my research life, this essay traces the encounters with cyclodextrins and polyrotaxanes, the development of slide-ring gels, and the establishment of a venture company for commercialization of slide-ring materials involving many people, various support systems and investments.

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事業化に向けた研究 Research for Commercialization

山村　雄一 Yuichi YAMAMURA

＜要旨＞ One of the missions of Mitsui Chemicals’ R&D program is to speed up the research and development and commercialization of products. To achieve this, inter-departmental cooperation is required.

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展望　COVER STORY: Highlight Reviews

プロピレンの立体特異的リビング配位重合 Stereospecific Living Coordination Polymerization of Propylene

塩野　毅・蔡　正国 Takeshi SHIONO and Zhengguo CAI

＜要旨＞構造の明確な金属錯体を基盤としたシングルサイト触媒の進歩は，特徴あるさまざまなオレフィンリビング重合系を生み出した。本稿では，配位重合でなければ不可能なプロピレンの立体特異的リビング重合についてこれまでの研究を概観し，代表的な立体規則性プロピレンブロック共重合体の合成例について述べる。また，高分子鎖と等モルの開始剤（触媒）を必要とするというリビング重合の最大の欠点を克服しうる，単分散ポリオレフィンの触媒的合成に関する試みについて紹介する。 Keywords: Ziegler-Natta Catalyst / Single-Site Catalyst / Living Polymerization / Stereospecific Polymerization / Propylene / Block Copolymer / Catalytic Polymerization

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ラジカル重合における配列制御 Sequence Control in Radical Polymerization

上垣外　正己・佐藤　浩太郎 Masami KAMIGAITO and Kotaro SATOH

＜要旨＞合成高分子におけるモノマー配列の制御は究極の課題である。本稿では，リビングラジカル共重合による分子量の制御された交互共重合体やグラジエント共重合体の合成，遷移金属触媒による逐次ラジカル重合を用いた配列制御ビニルポリマーの合成など，ラジカル重合における配列制御の最近の研究例を紹介する。 Keywords: Radical Polymerization / Living Polymerization / Monomer Sequence / Alternating Copolymer / Gradient Copolymer / Vinyl Polymer

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不斉液晶反応場での重合とその展開 Development of Polymerization in Asymmetric Liquid Crystal Reaction Field: Synthesis of Helical Polyacetylene and Precision Control of Its Helical Structure

高　文柱・赤木　和夫 Munju GOH and Kazuo AKAGI

＜要旨＞キラルネマチック液晶を溶媒とする不斉液晶反応場での重合により，共役系高分子のらせん構造を精密に制御できることが明らかにされつつある。本稿では，不斉液晶反応場を用いたらせん状共役系高分子の合成と，そのらせん構造の精密制御について最近の研究進展を概説する。 Keywords: Conjugated Polymer / Helical Polyacetylene / Asymmetric Reaction Field / Chiral Nematic Liquid Crystal / Chiral Inversion / Hierarchical Structure / Binaphthyl Derivative / Cis-Rich Helical Polyacetylene

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トピックス　COVER STORY:Topics and Products

遷移金属錯体を開始剤とするジアゾ酢酸エステルの重合 Polymerization of Diazoacetates Initiated with Transition Metal Complexes

井原　栄治 Eiji IHARA

＜要旨＞ High molecular weight syndiotactic poly(ethoxycarbonylmethylenes) were prepared by Rh-initiated polymerization of ethyl diazoacetate. (NHC) Pd/borate systems were effective for the polymerization of diazoacetates with a variety of ester groups. Keywords: Diazoacetate / Rh Complex / Pd Complex / Poly (Substituted Methylene) / Stereoselective Polymerization

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化学選択的重縮合による“RAFT ゲル”の創発 Emergence of Gelationous Chain Transfer Agents “RAFT Gel”s via Chemoselective Polycondensation

高須　昭則・山本　研 Akinori TAKASU and Ken YAMAMOTO

＜要旨＞ Scandium trifluoromethanesulfonate [Sc(OTf)3]-catalyzed chemoselective dehydration polycondensations of thiomalic acid (TMA) with several diols afforded linear polyesters having pendant mercapto groups (Mn > 1.0 × 104). We also demonstrated cross-linkings of the pendent mercapto groups using thiocarbonyldiimidazole (TCDI) to prepare gelationous chain transfer agents “RAFT Gel”s. Keywords: Polyester / Chemoselective Dehydration Polycondensation / Mercapto Group / Reversible Addition-Fragmentation Chain Transfer (RAFT) Polymerization / Gelationous Chain Transfer Agents “RAFT Gel”s

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ジエン，シクロオレフィンの異性化重合制御　―新しい高分子の合成と集合機能― Controlled Isomerization Polymerization of Dienes and Cycloolefins: Synthesis and Aggregation Behaviors of the New Polymers

竹内　大介・小坂田　耕太郎 Daisuke TAKEUCHI and Kohtaro OSAKADA

＜要旨＞ Diimine Pd complexes promote isomerization polymerization of 1,6-dienes and cyclopentenes to result in polymers composed of cyclopentane and an oligomethylene spacer. The isotactic polymers of 4-alkylcyclopentenes show liquid crystalline properties. Keywords: Diene / Cycloolefin / Pd Complex / Isomerization Polymerization / Cyclopolymerization / Stereoselective Polymerization / Liquid Crystalline

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エポキシドと二酸化炭素との精密交互共重合 Precision Copolymerization of Epoxides with Carbon Dioxide

中野　幸司・野崎　京子 Koji NAKANO and Kyoko NOZAKI

＜要旨＞ Copolymerization of propylene oxide (PO) with CO2 was investigated by using cobalt (III) complexes bearing piperidinium end-capping arm (s). The catalyst system can selectively produce poly (propylene carbonate) (PPC) even at complete conversion of PO. Regio- and enantiomer-selective copolymerization resulted in stereogradient-type PPC. Keywords: Epoxide / Carbon Dioxide / Copolymerization / Regioregularity / Stereoregularity

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有機触媒を用いたリビングラジカル重合 Living Radical Polymerizations with Organic Catalysts

後藤　淳 Atsushi GOTO

＜要旨＞ Living radical polymerizations (LRPs) using organic (P, N, O, and C-centered) catalysts were developed. The catalysts include such common compounds as phosphites (P), amines (N), phenols (O), and dienes (C). Attractive features of the LRPs include good environmental safety, low cost, and robustness. Keywords: Living Radical Polymerization / Organic Catalysts / Phosphorus / Nitrogen / Oxygen / Carbon

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リビングラジカル重合技術を用いた事業化最前線 The Forefront of Materials Synthesized by Living Radical Polymerization

亀島　隆 Takashi KAMESHIMA

＜要旨＞ The polymers synthesized by living radical polymerization have a wide potential application in various areas, and the recent progress of research has enabled the polymerization method to be scaled up for commercial production. Living radical polymerization technology has the possibility to create a new business field by providing new functional materials. Keywords: Living Radical Polymerization / TERP / Block Copolymer / Nanotechnology / Pressure Sensitive Adhesives

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イミン，ヒドラゾン結合を有する動的共有結合高分子 Covalent Dynamic Polymers Based on C=N Bonds in Imines and Hydrazones

藤井　俊介・小野　隆 Shunsuke FUJII and Takashi ONO

＜要旨＞ The presented topics concern both basic and applied research on covalent dynamic polymers based on C=N bonds in imines and hydrazones, capable of responding to physical triggers or to chemical effectors by modification of their very constitution, and thus constitute a new class of adaptive, “intelligent” materials. Keywords: Dynamic Covalent Bonds / Dynamic Polymers / Adaptive Materials

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高分子科学最近の進歩　Front-Line Polymer Science

電子ペーパーにおける高分子材料の役割 Role of Polymer Materials in Electronic Paper

樋口　昌芳 Masayoshi HIGUCHI

＜要旨＞ Electronic paper, which can hold images even after the power is turned off, has received much attention as next generation’s display, because it will contribute energy- and resource-saving. An electrophoretic style of electronic paper is already commercially available as electronic books such as the “Kindle™”, but now colorization of electronic paper is one of the biggest topics. It is considered that an electrochromic style of electronic paper is a promising way to achieve the colorization. Many electrochromic materials have been reported so far. Especially, organic-metallic hybrid polymers formed by the complexation of metal ions as Fe(II) or Ru(II) with bis(terpyridine) ligands have specific colors based on metal-to-ligand charge transfer (MLCT) absorption and were revealed to show electrochromic properties by electrochemical redox reactions of the metal ions. Multicolor electrochromic change was also achieved by the introduction of two types of metal ions into the polymer. New polymer materials such as organic-metallic hybrid polymers may open the next door toward ultimate paper-like displays. Keywords: Electronic Papers / Electrochromic Properties / Organic-Metallic Hybrid Polymers / Metallo-Supramolecular Polyelectrolytes / Multicolor / Solid-State Devices / Smart Windows

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