| 高分子 Vol.65 No.9 |
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特集 高分子合成：生まれ変わる手法、引き継がれる反応の基本
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| 展望 COVER STORY: Highlight Reviews |
| 精密ラジカル重合による機能性高分子 Functional Polymers via Precision Radical Polymerization: Cutting Edge in Primary Structure Control and Self-Assembly |
寺島 崇矢・澤本 光男 Takaya TERASHIMA, Mitsuo SAWAMOTO |
| ＜要旨＞リビングラジカル重合は、多種多様なモノマーに適用できるため、機能性高分子を合成するうえできわめて有用なツールである。本稿では、このリビングラジカル重合に異種反応や分子認識を組み合わせ、精密な一次構造制御を実現する高分子合成や、ランダム共重合体を用いた精密な自己組織化など、最近の新展開について紹介する。 Keywords: Functional Polymer / Living Radical Polymerization / Tandem Catalysis / Primary Structure / Sequence Control / Self-Assembly / Folding / Amphiphilic |
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| 高分子反応で得られる共重合体の連鎖解析と連鎖制御 Monomer Sequence Analysis of Copolymers Obtained by Various Polymer Reactions |
右手 浩一・平野 朋広 Koichi UTE, Tomohiro HIRANO |
| ＜要旨＞ ホモポリマー側鎖の部分的化学変換により、種々の連鎖構造の共重合体が得られる。この際、主鎖の切断や組み換えがなければ、元のポリマーの重合度や立体規則性は保持される。本稿では、このような高分子反応を利用した共重合体の連鎖制御と、そのツールとなる連鎖解析の方法について述べる。 Keywords: NMR Spectroscopy / Multivariate Analysis / Average Sequence Length / Persistence Ratio / Hydrolysis / Catalytic Hydrogenation / Transesterification / Neighboring Group Effect |
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| 配位・メタセシス重合の新展開と展望 Recent Progress in Olefin Coordination/ Metathesis Polymerization |
野村 琴広 Kotohiro NOMURA |
| ＜要旨＞ オレフィンの配位重合とメタセシス重合、とくに前周期遷移金属錯体触媒による配位重合を利用した新規ポリオレフィン（嵩高いオレフィンや環状オレフィンとの共重合体、反応性の官能基を有するポリマー）の合成やオレフィンメタセシス重合における立体特異性制御のための触媒開発に関する最近の成果をまとめた。 Keywords: New Polyolefins / Complex Catalysts / Coordination Polymerization / Metathesis / ROMP / Cyclic Olefin Copolymers / Titanium / Vanadium |
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| トピックス COVER STORY: Topics and Products |
| 置換ポリアセチレンの精密合成 Precise Synthesis of Substituted Polyacetylenes |
三田 文雄 Fumio SANDA |
| ＜要旨＞ Substituted polyacetylenes have received considerable attention, owing to their properties resulting from the π-conjugated backbone such as photoconductivity and electroluminescence. The introduction of functional groups at the side chains provides polyacetylenes with useful structural features including liquid crystallinity, molecular recognition, stimuli-responsiveness, and gas permeability. Substituted polyacetylenes are synthesized by the polymerization of the corresponding acetylene monomers using transition-metal catalysts. Rh catalysts bearing a triphenylvinyl group polymerize substituted acetylene monomers in a living fashion to give polymers with controlled molecular weights, geometry and end structures. Pd catalysts bearing bulky phosphine ligands polymerize disubstituted acetylene monomers via the coordination-insertion mechanism. Substituted polyacetylenes bearing chiral substituents adopt helical conformations, whose predominant screw sense transforms between right- and left-handed in CHCl3/MeOH with respect to the solvent composition. The polymers prefer conformations with large dipole moments in polar media, confirmed by the semi empirical molecular orbital calculations, COSMO method. Keywords: Higher Order Structure / Optically Active Polymer / Palladium Catalyst / Polyacetylene / Rhodium Catalyst |
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| Pd錯体を開始剤とするジアゾ酢酸エステルの重合の新展開 New Developments of Pd-Initiated Polymerization of Diazoacetates |
下元 浩晃・井原 栄治 Hiroaki SHIMOMOTO, Eiji IHARA |
| ＜要旨＞ Recent developments of Pd-initiated polymerization of diazoacetates are described. Polymerization of diazoacetates is a useful method for preparing C-C main chain polymers bearing an ester substituent on each main chain carbon atom [poly(substituted methylene)s]. However, the substituents introduced into the side chain were limited to hydrophobic groups, and controlled polymerization has not been achieved so far. Recently, we have successfully synthesized poly(substituted methylene)s with hydrophilic groups including hydroxy group and oligo(ethylene glycol) units. The resulting polymers were found to show higher hydrophilicity compared to the corresponding vinyl polymer counterparts. In addition, we have succeeded in controlling the polymerization of diazoacetates for the first time by employing cyclophosphazene-containing diazoacetates as monomers. Keywords: Pd Complex / Diazoacetate / Hydroxy Group / Oligo(ethylene glycol) / LCST-Type Phase Separation / Controlled Polymerization / Cyclotriphosphazene |
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| 放射光X線吸収分光を利用した重合反応機構の解明 Elucidating the Mechanism of Polymerization using Synchrotron X-Ray Absorption Spectroscopy |
平井 智康 Tomoyasu HIRAI |
| ＜要旨＞ Polymerization of 3-hexylthiophene (3HT) with FeCl3 is simple, efficient, and has been widely adopted for both laboratory and industrial scale production purpose. However, there remains considerable debate regarding the polymerization mechanism. We have used partial fluorescence yield X-ray absorption fine structure (XAFS) techniques to monitor the change in valence state of the solid FeCl3 particles in CHCl3 and hexane. The FeCl3 acts as a catalyst when the reaction is performed in CHCl3, but behaves as an oxidant in hexane. The catalytic behavior is attributed to the decomposition of CHCl3, which has been previously reported to oxidize Fe2+ to Fe3+. This is the first report on the catalytic role of FeCl3 during the polymerization of 3HT in CHCl3. Keywords: Synchrotoron Radiation / Reaction Mechanism / X-Ray Absorption Fine Structure (XAFS) / Catalysts |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| 大きな振れ幅で創造的な研究を Keep Multifarious Vibes to Do Creative Study |
敷中 一洋 Kazuhiro SHIKINAKA |
| ＜要旨＞ To do creative studies, I keep it in my mind to experience various things in accordance with ancestors’ wisdom. As a result, I can get “multifarious vibes for various scientific topics”, which will let me experience a rich and fruitful researcher’s life. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| π電子系の広がりをもつ高分子材料の合成と応用 Synthesis and Applications of Polymers Possessing Extended -Electronic Systems |
冨田 育義・西山 寛樹・松村 吉将 Ikuyoshi TOMITA, Hiroki NISHIYAMA, Yoshimasa MATSUMURA |
| ＜要旨＞ Recent progress in the synthesis of polymers possessing extended π-electronic systems is reviewed. That is, polymers possessing through space π-electronic interactions and those having π-conjugated systems along the main chain are focused from the viewpoint of polymer synthetic chemistry. Regarding the synthesis of π-conjugated polymers, new methods such as the catalyst-transfer polymerizations, the direct arylation polycondensations, the three-component polycondensations, and the main chain-transformations of the organometallic polymer precursors are described. Some characteristics of the polymers obtained by these methods are also briefly described. Keywords: π-Conjugated Polymers / Polycondensation / Catalyst-Transfer Polymerization / Direct Arylation / Polymer Reaction / Organometallic Polymer |
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