| 高分子 Vol.68 No.11 |
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特集 末端の最先端
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| 展望 COVER STORY: Highlight Reviews |
| テレケリックポリマー製品群とその用途 Telechelic Polymer Products and their Applications |
中川 佳樹 Yoshiki NAKAGAWA |
| ＜要旨＞ 低Tg主鎖の両末端に架橋性官能基を有するテレケリックポリマーは、ポリマー末端構造を工業的に利用した代表例である。末端官能基が反応して網目構造となり、ゴム特性を与える。カネカは、ポリエーテル、ポリイソブチレン、ポリアクリレート主鎖のテレケリックポリマーを、制御重合技術を用いて開発し、これらは多様な用途で使用されている。 Keywords: End Functional Group / Telechelic / Polyether / Polyisobutylene / Polyacrylate / Controlled Polymerization / Sealant / Adhesive |
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| からみあった高分子のダイナミクスにおける末端の役割 Role of Chain Ends in Dynamics of Entangled Polymers |
畝山 多加志 Takashi UNEYAMA |
| ＜要旨＞ からみあった高分子中での高分子鎖の運動において、末端がどのような役割をもつか議論する。高分子鎖が自分に沿って動くレプテーション運動においては末端が重要な役割を果たしていると解釈できる。また、高分子鎖重心の運動と末端運動の関係と、重心運動から末端運動の情報を得る方法を示す。 Keywords: Entangled Polymer / End-to-End Vector / Reptation / Diffusion |
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| 半導体高分子の末端修飾と有機電子デバイスでの機能発現 End-Functionalization of Semiconducting Polymers and Their Functions in Organic Devices |
但馬 敬介 Keisuke TAJIMA |
| ＜要旨＞ 半導体高分子の薄膜を用いた電子デバイスは、印刷で作製できるフレキシブルエレクトロニクスへの展開から大きな注目を集めている。材料を設計するうえで、半導体高分子の末端構造は、デバイス性能に無視できない影響をもっている。ここでは、半導体高分子の末端構造の制御と薄膜中の構造への影響、および有機電子デバイスへの応用について紹介する。 Keywords: Semiconducting Polymers / Thin Films / Organic Electronics / Polymerization / Interface Modification / Self-Organization / Crystallization |
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| トピックス COVER STORY: Topics and Products |
| 二次元自己集合化能をもつ三脚型トリプチセンの高分子末端ユニットとしての効果 Terminal-Group Effect of a Triptycene Derivative that has a Dominant Influence on the Physical Properties of a Polymer |
石割 文崇・福島 孝典 Fumitaka ISHIWARI, Takanori FUKUSHIMA |
| ＜要旨＞ A surprising terminal-group effect on the assembly and rheological properties of PDMS is described. We have recently demonstrated that 1,8,13-trisubstituted and 1,8-disubstituted triptycenes show remarkable self-assembly behavior resulting in a highly ordered “2D＋1D” structure based on nested hexagonal packing of the three blades of triptycene. We found that when a 1,8-disubstituted triptycene is attached to the termini of a liquid polydimethylsiloxane (PDMS, Mn = 18－24 kDa), a highly viscous solid polymer with birefringence is obtained. Surprisingly, the telechelic PDMS, despite a low content of the triptycene termini (6 wt%) and a large distribution of Mw/Mn (ca. 2), can form a well-ordered “2D＋1D” structure, where layers of the PDMS domains that are formed between 2D triptycene arrays stack into a 1D multilayer structure with a layer spacing of 18－20 nm. Consequently, the complex viscosity of the telechelic PDMS was dramatically enhanced. Notably, PDMS functionalized with 1,4-disubstituted triptycenes, hardly form such an ordered structure. Keywords: Spuramolecular Polymers / Self-Assembly / Tripodal Triptycene / Terminal Effect / PDMS |
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| ラベル法で解明する高分子末端のダイナミクス Dynamics of the Polymer Chain End |
三輪 洋平・沓水 祥一 Yohei MIWA, Shoichi KUTSUMIZU |
| ＜要旨＞ The chain end is present as unique local structure in polymers; the chain end often affects the physical properties of polymeric materials. On the other hand, the quantitative physical property of the chain end is still unclear. Here, the molecular motion at the chain end of polystyrene (PS) has been studied by the combination of three kinds of labeling techniques: spin-, dielectric-, and deuterium-labeling. The segmental mobility at chain end above the glass transition temperature (Tg) was determined by electron spin resonance measurement with the spin-labeling and dielectric spectroscopy with dielectric-labeling. The segmental mobility at the chain end is roughly double compared to that at the midchain sites at Tg＋50 K. On the other hand, the local Tgs at the regions around the chain end and midchain site determined by the spin-labeling and FT-IR with deuterium-labeling techniques were comparable with each other. This result reveals that the chain ends move cooperatively with numerous neigboring other segments around the Tg. Keywords: Chain End / Labeling / Electron Spin Resonance / Dielectric Spectroscopy / FT-IR / Glass Transition Temperature / Segmental Mobility |
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| 末端変性ポリマーを用いたゴム材料中のシリカ分散性制御 Control of Silica Dispersibility Using End-Modified Polymer |
曽根 卓男 Takuo SONE |
| ＜要旨＞ The reduction of rolling resistance of tires has become a more important aspect of the tire development. Rolling resistance is primarily related to the hysteresis loss in the tire tread compounds and silica has been widely used in them. The dispersibility of silica is considered to affect hysteresis loss. Some modified styrene butadiene rubbers (SBRs) with functional groups at the polymer chain ends have been prepared by living anionic polymerization. They showed significant reduction in the hysteresis loss of rubber compounds by achieving interaction with silica. To investigate the hierarchical structure of the silica filler in rubber compounds with modified SBR small angle X-ray scattering (SAXS) was used. The distribution of particle size of silica aggregates can be obtained by the analysis of the scattering profile, and the result was that the radius of the silica aggregate is smaller and the distribution of particle size is narrower in modified SBR as compared to non-modified SBR. Keywords: End-Modified SBR / Living Polymerization / Rubber Compound / Silica Dispersion / SPring-8 / Reverse Monte Carlo Method |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| 天使と悪魔 Angels & Demons |
野々山 貴行 Takayuki NONOYAMA |
| ＜要旨＞ We do not know what will happen in the future. There are many events that we cannot control ourselves. However, your future leads not only to darkness but also to light. Be optimistic for your life. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| 環状高分子合成の進展と機能材料への可能性 Progress of Cyclic Polymer Synthesis and Potentials to Functional Materials |
山本 拓矢 Takuya YAMAMOTO |
| ＜要旨＞ The basic properties of cyclic polymers were comprehensively studied, and the synthesis of not only monocyclic but also multicyclic homopolymers and copolymers has been established. Comprehensive and rigorous investigations on topology effects are currently in progress. In particular, it is worth noting that more and more studies are focused on topology effects on various self-assembled states, i.e., micelles, gels, LB films, etc. These studies indicate that the topology effects derived from the difference between linear and cyclic can be amplified by self-assembly. It was also reported that reversible linear–cyclic topological conversion was succeeded, and special characteristics were found in π-conjugated cyclic polymers. Keywords: Cyclic Polymer / Self-Assembly / Amphiphile / Reversible Topological Conversion / π-Conjugated Polymer |
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