高分子 Vol.61 No.11
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特集 高分子反応の新展開 -精密制御から材料設計まで-
展望 COVER STORY: Highlight Reviews
Photoinitiated Click Reactions for the Creation of Spatially Defined Materials Daigo MIYAJIMA, Masahito MURAI and Craig Jon HAWKER
<要旨> Photoinitiated click reactions possess significant advantages over traditional click reactions as they allow for spatial and temporal control. This enables the formation of patterned or gradient surfaces with specific substrates, controlled attachment of biological entities, etc.. In this minireview, we highlight the latest progress on photoinitiated click chemistry and demonstrate the future potential of this emerging area.
Keywords: Click Chemistry / Patterning / Photochemistry / Thiol-Ene / CuAAC / Polymer Chemistry / Materials Synthesis
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分解性を有する架橋・硬化ポリマーの合成と応用
Synthesis and Application of Crosslinked Polymers with Degradable Property
白井 正充
Masamitsu SHIRAI
<要旨> 架橋・硬化ポリマーは、優れた機械的強度や高耐熱性を有する材料であり、従来から広く使われている。このような材料に分解性を付与すると、これまでとは違った新しい材料設計が可能になる。本稿では、分解性を有する架橋・硬化ポリマーの設計・合成と材料としての応用について、最近の研究を紹介する。
Keywords: Multifunctional Monomer / Crosslinked-Polymer / Degradation / Environmentally Friendly Materials / Reworkable Materials / Self-Healing
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多糖類水酸基の選択的誘導体化による機能発現
Functionalization of Polysaccharides through Selective Derivatization
大西 敦・柴田 徹
Atsushi OHNISHI, Tohru SHIBATA
<要旨> セルロースなどの多糖類は古くから人類に利用されてきた天然由来材料であるが、近年、多糖水酸基誘導体化技術の進展により新たな機能性が見出され注目されている。高分子化合物であり、かつ3官能性のセルロース類の反応の概観および一例としてキラル識別機能について、新たな機能性付与の方法および効果を解説する。
Keywords: Cellulose / Amylose / Regioselective / Substitution / Functionalyzation / Chiral Stationary Phase
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トピックス COVER STORY: Topics and Products
鎖末端にクリック反応性官能基を有する高分子の精密合成と機能性高分子への応用
Precise Synthesis of Polymers End-Functionalized with Clickable Functional Groups and Their Application to Preparation of Functional Polymers
覚知 豊次・渕瀬 啓太
Toyoji KAKUCHI, Keita FUCHISE
<要旨> The combination of controlled/living polymerizations and click reactions has realized the synthesis of polymers with various structures. Our group has developed precise synthesis methods for polyester, polyether, poly(n-hexyl isocyanate), and polyacrylamides end-functionalized with clickable functional groups, such as an azido group, an ethynyl group, and so on. The end-functionalized poly(N-isopropylacrylamide) and its block copolymer have been applied to development of functional polymers.
Keywords: Controlled/Living Polymerization / Click Reaction / End-Functionalized Polymers / Polyesters / Polyethers / Poly(n-hexyl isocyanate) / Polyacrylamides / Thermoresponsive Polymers
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高分子間クリック反応と高分子内クリップ反応を用いる多環トポロジー高分子の合成
Intermolecular Click and Intramolecular Clip Process for Constructing Multicyclic Polymer Topologies
菅井 直人・手塚 育志
Naoto SUGAI, Yasuyuki TEZUKA
<要旨> Cyclic and multicyclic polymers have gained increasing attention due to their unique functions arisen from their topology effects. In this account, a new synthetic protocol to construct complex multicyclic polymer topologies is outlined by employing intermolecular click and intramolecular clip process using a variety of cyclic or multicyclic precursors having prescribed functional groups. A variety of complex polymer topologies has been constructed, including bridge- and spiro- as well as fused-type tricyclic or tetracyclic forms with programmed folding structures.
Keywords: Cyclic Polymer / Topological Polymer Chemistry / Click Chemistry / Olefin Metathesis / Electrostatic Self-Assembly and Covalent Fixation
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TCNE-アルキン付加反応に基づく新規芳香族系高分子の合成と光電子機能の評価
Click Synthesis and Optoelectronic Properties of Novel Aromatic Polymers
道信 剛志
Tsuyoshi MICHINOBU
<要旨> p-Type semiconducting polymers were post-functionalized by the click chemistry-type addition reaction between electron-rich alkynes and acceptor molecules. For example, the addition of tetracyanoethylene (TCNE) to aromatic polyamines bearing electron-rich alkynes formed donor-acceptor chromophores with low energy charge-transfer bands. Electrochemistry measurements revealed that the polymer energy levels decreased as more TCNE were added. The thin film transistors of these polymers were fabricated, and it was demonstrated that there is a clear correlation between the polymer energy levels and hole mobilities.
Keywords: Click Chemistry / Donor-Acceptor Systems / Charge-Transfer / Aromatic Polymers / Electrochemistry / Mobility / Thin Film Transistor
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高分子反応を利用したエンプラへの感光性付与:反応現像画像形成法
Addition of Photosensitivity to Engineering Plastics Utilizing Polymer Reaction: Reaction Development Patterning
大山 俊幸
Toshiyuki OYAMA
<要旨> Conventional photosensitive polymides (PSPIs) have disadvantages such as necessity of high temperature post-curing after pattern formation due to their use of polyimide precursors, poly(amic acid)s, as polymer components. We have developed a novel mechanism, reaction development patterning (RDP), to give photosensitivity to polyimides and other engineering plastics. Pattern formation by RDP is based on selective change in solubility of engineering plastics at photo-irradiated (or unirradiated) areas by nucleophilic acyl substitution between carboxylic-acid derivatives in a polymer chain and nucleophiles in a developer during development process. Thus, RDP-based PSPIs are obtained from polyimides themselves, and pattern formation from polycarbonates and polyesters is also achieved by papplying RDP to these polymers.
Keywords: Photosensitive Polyimide / Photosensitive Engineering Plastics / Nucleophilic Acyl Substitution / Diazonaphthoquinone / Development by Alkaline Solution
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高分子反応の設計に基づく易解体性接着材料の開発
Development of Dismantlable Adhesion Materials Based on Design of Polymer Reactions
松本 章一
Akikazu MATSUMOTO
<要旨> We have demonstrated the validity of a new type of pressure-sensitive adhesion system using block copolymers containing the low glass transition poly(2-ethylhexyl acrylate) or poly(n-butyl acrylate) segment and the reactive poly(tert-butyl acrylate) (PtBA) segment in the presence of a photoacid generator. This adhesion system can be easily debonded due to a change in the polymer properties of the adhesives by acid-catalyzed deprotection uniquely occurring during the photoirradiation followed by postbaking. The block copolymers with a well-defined molecular structure were
synthesized by living radical polymerization, such as atom transfer radical polymerization and organotellurium-mediated living radical polymerization and their adhesive properties were evaluated using the 180・peel test. A drastic change in the adhesive strength of the block copolymers was observed in response to the dual external stimuli consisting of UV irradiation and the subsequent heating.
Keywords: Block Copolymer / Controlled Polymerization / Deprotection / Dismantalble Adhesion / Living Radical Polymerization / Photoacid Generator / Polyacrylate / Pressure-Sensitve Adhesive
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高分子科学最近の進歩 Front-Line Polymer Science
無機高分子の新展開:無機元素ブロック高分子材料へ
Development of Inorganic Polymers: To Inorganic-Element-Block Polymers
中 建介
Kensuke NAKA

<要旨> Thanks to meet organic-inorganic polymer hybrids with recent development of nano-sized inorganic blocks, single component polymer hybrids or matrix-free nanocomposites have been proposed. This kind of materials is regarded as “Inorganic-element-block polymers”, which is an extended concept of “organic-inorganic hybrid polymers”. This review describes recent development of the Inorganic-element-block polymers, mainly focusing on the synthesis of polyhedral oligosilsesquioxane derivatives and their solid-state properties. Examples of inorganic nanoparticle hybrids are also introduced.
Keywords: Inorganic-Element-Block Polymers / Single Component Polymer Hybrids / Matrix-Free Nanocomposites / Polyhedral Oligosilsesquioxane / Inorganic Nanoparticle Hybrids / Inorganic Polymers / Organic-Inorganic Hybrids

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グローイングポリマー Polymer Science and I: A Personal Account
プロの研究者として
As a Professional Researcher
平井 智康
Tomoyasu HIRAI
<要旨> I would like to contribute substantially to the society, on the basis of my skills and the knowledge that I have gained.
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