| 高分子 Vol.62 No.5 |
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特集 精密重合の開発と実用化
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| 展望 COVER STORY: Highlight Reviews |
| FI触媒によるオレフィンポリマーの構造制御と機能性材料への展開 FI Catalysts: New Olefin Polymerization Catalysts for the Creation of Value-Added Olefin-Based Materials |
三谷 誠・藤田 照典 Makoto MITANI, Terunori FUJITA |
| ＜要旨＞ 三井化学（株）が開発したポストメタロセン触媒「FI触媒」は高活性であるのみならず、従来の触媒では達成が困難であったオレフィンポリマーの精密構造制御をも可能とした。FI触媒のポリマー構造制御技術をベースとして、差別化された物性をもつ種々の機能性オレフィンポリマーが開発されている。 Keywords: Olefin Polymerization / Postmetallocene Catalysts / FI Catalysts / Polyolefins |
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| リビングカチオン重合を用いた機能性材料への挑戦 New Generation Functional Polymers by Living Cationic Polymerization |
青島 貞人・金澤 有紘 Sadahito AOSHIMA, Arihiro KANAZAWA |
| ＜要旨＞ 近年、未来へ向けた機能性材料が次々と創製されているが、これまでカチオン重合を用いた検討例は限られていた。昨今ようやく、特有の合成法・新規モノマーの開拓、反応の精密制御法が大きく進展し、リビングカチオン重合による本格的な機能性材料への挑戦が始まってきた。本稿では、最近の例を挙げるとともに今後の可能性に関して概説する。 Keywords: Cationic Polymerization / Living Polymerization / Functional Polymer / Stimuli-Responsive Polymer / Thermosensitive Polymer |
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| 触媒移動型連鎖縮合重合によるπ共役系高分子の精密合成 Precision Synthesis of π-Conjugated Polymers by Catalyst-Transfer Condensation Polymerization |
野嶋 雅貴・太田 佳宏・横澤 勉 Masataka NOJIMA, Yoshihiro OHTA, Tsutomu YOKOZAWA |
| ＜要旨＞ π共役系高分子は現在最も注目されている有機エレクトニクス材料の一つであるが、重縮合によって合成されるため、分子量や末端構造を制御して合成するのは困難であった。本稿では、π共役系高分子をリビング重合のように合成できる触媒移動型連鎖縮合重合（CTCP）の開発とその一般性、最近の展開について紹介する。 Keywords: π-Conjugated Polymer / Catalyst-Transfer Condensation Polymerization |
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| トピックス COVER STORY: Topics and Products |
| 新規炭化水素系モノマーのリビングアニオン重合 Living Anionic Polymerization of Novel Hydrocarbon Monomers |
石曽根 隆 Takashi ISHIZONE |
| ＜要旨＞ Anionic polymerizations of a series of hydrocarbon monomers were investigated to confirm their polymerizability. Anionic polymerization of 1,4-divinylbenzene proceeded with organolithium initiator in the presence of potassium tert-butoxide in THF to give a soluble polymer with predicted molecular weight and very narrow molecular weight distribution (Mw/Mn < 1.1). A serious side reaction such as cross-linking was sufficiently suppressed by the effect of added salts. Living anionic polymerizations of 4-(1-adamantyl)styrene and 2-(1-adamantyl)-1,3-butadiene were realized to afford well-defined polymers showing high glass transition temperatures at 234 and 106 ℃, indicating the effect of introduced adamantyl group on thermal property. Exomethylene hydrocarbon monomers such as α-methyleneindane, α-methylenetetralin, and benzofulvene (α-methyleneindene) smoothly underwent the anionic polymerizations with organolithium and organopotassium initiators to form tailored polymers. The anionic polymerizations of benzofulvene gave a polymer containing 1,2-and 1,4-addition modes and could be initiated with low nucleophilic initiators such as Grignard reagent, alkoxide, and living poly(alkyl methacrylate), indicating the extremely high anionic polymerizability. Keywords: Living Polymer / Anionic Polymerization / Hydrocarbon Monomers / 1,4-Divinylbenzene / 4-(1-Adamantyl)styrene / 2-(1-Adamantyl)-1,3-butadiene / α-Methyleneindane / Benzofulvene |
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| S-ビニルモノマー類のリビングラジカル重合を用いた機能性高分子の精密合成 Precise Synthesis of Functional Polymers by Living Radical Polymerization of S-Vinyl Monomers |
森 秀晴 Hideharu MORI |
| ＜要旨＞ Recent significant progress of controlled radical polymerization has allowed for the synthesis of well-defined functional polymers by radical polymerization of non-conjugated monomers. We recently developed the controlled synthesis of sulfur-containing polymers by reversible addition-fragmentation chain transfer (RAFT) polymerization of non-conjugated S-vinyl monomers. Differing from styrene, (meth)acrylate, and (meth)acrylamide-type monomers, the direct linkage of the sulfur atom to the vinyl group is an important feature of these monomers, because it may affect not only the polymerization behavior but also various properties of the resulting polymers. Sulfonic acid-containing polymers and thermoresponsive-ionic block copolymers were obtained by RAFT polymerization of vinyl sulfonate esters using a suitable xanthate-type chain transfer agent, followed by deprotection. RAFT polymerization of S-vinyl sulfide derivatives having aromatic rings were found to proceed in controlled fashions. Incorporation of optoelectronic groups on the halogen moiety of the polymers derived from S-vinyl sulfides with halophenyl groups afforded novel functional polymers with characteristic properties. Keywords: RAFT Polymerization / S-Vinyl Monomer / Sulfur-Containing Polymer / Non-Conjugated Monomer / Block Copolymer / Xantate-Type Chain Transfer Agent |
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| リビングカチオン重合によるイソブチレン系重合体の研究開発と実用化 Polyisobutylene Based Polymers by Living Cationic Polymerization: Research, Development and Industrialization |
山中 祥道・木村 勝彦 Yoshimichi YAMANAKA, Katsuhiko KIMURA |
| ＜要旨＞Kaneka has led in the industrialization of living cationic polymerization. Kaneka started running the first industrial process using living cationic polymerization for the production of isobutylene in 1997. The technology of block copolymerization of isobutylene and styrene in living fashion has also been developed at our company. Our current products are the telechelic oligomers “EPION®” and the thermoplastic elastomers “SIBSTAR®”. This report traces the history of the development of the living polymerization technology at Kaneka. Keywords: Living Cationic Polymerization |
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| リビングアニオン重合に基づく微細加工向け誘導自己組織化技術の開発 Directed Self Assembly Technology with the Polymers Prepared by Living-Anionic Polymerization for Fabrications of Finer Patterns |
山口 佳一 Yoshikazu YAMAGUCHI |
| ＜要旨＞ Demand for high performance chips has drastically increased due to the development of smart phones, tablet-PCs and so on. Most “State of the art” Fabs have implemented ArF immersion technology today. Double patterning, double exposure, and side-wall image transfer technology allow for the extension of ArF immersion into 2x nm half-pitch (hp) application. In order to fabricate finer patterns, it is necessary to develop new processes, such as EUV, EB, Nano imprint and Directed Self Assembly (DSA). It is possible to fabricate patterns with less than 20 nmhp by combining DSA and the other technologies. In this paper, the application of DSA for semiconductor manufacturing is introduced. 8 nmhp line and space (L/S) pattern and 15 nm hole pattern are obtained with a block copolymer system and 19 nm L/S pattern was obtained with a blending polymer system. These results have promising potentials for the fabrications of finer patterns. Keywords: Directed Self Assembly / DSA / Semiconductor / Lithography / Block-Copolymer / Blending / χ-Parameter |
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| ニトロキシドに基づくリビングラジカル重合の開発と実用化 Development and Industrialization of Nitroxide Based Living Polymerization |
有浦 芙美 Fumi ARIURA |
| ＜要旨＞ Over a span of 20 years, Arkema has developed nitroxide based controlled radical polymerization (CRP) technology. The principal motivation was to develop a CRP catalyst which can be applied to industrial polymer production. After lots of studies, we discovered an alkoxyamine consisting of stable nitroxide, which is called BlocBuilder® MA. Arkema has also developed other ranges of CRP products based on BlocBuilder® MA. Nanostrength® is triblock block copolymer, PMMA-b-PBA-b-PMMA. It is known as a high performance impact modifier of epoxy resin. Flexibloc® is a living polymer which can be reactivated in the polymerization from its chain end. It allows users to synthesize CRP polymers without special treatment such as removal of residual monomer. On the other hand, Arkema’s subsidiary company, Altuglas® International had successfully proven the further possibility of CRP technology. PMMA cast sheet modified BlocBuilder® MA based elastomer showed well-organized nanostructure in the bulk. This cast sheet shows higher impact resistance, good transparency and remarkable chemical resistance. Keywords: CRP / Nitorixide / Polymer Design / Industrialization / Block Copolymer / Living Polymer / Nanostructure |
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| グローイングポリマー Polymer Science and I: A Personal Account |
| Explore Chemistry！ | 小門 憲太 Kenta KOKADO |
| ＜要旨＞ “Enjoy Chemistry!” is the slogan of my supervisor, Prof. Chujo. This personal account traces my exploration of chemistry, toward the world of “enjoy chemistry”. |
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| 高分子科学最近の進歩 Front-Line Polymer Science |
| 精密ラジカル重合の展開 反応制御と機能性分子鎖の精密構築 Cutting-Edge in Precision Radical Polymerization: Advanced Reaction Control and Functional Macromolecular Chains |
大内 誠・寺島 崇矢・澤本 光男 Makoto OUCHI, Takaya TERASHIMA, Mitsuo SAWAMOTO |
＜要旨＞ This short account focuses on some cutting-edge topics and develpoments in metal-mediated precision/living radical polymerization, apart from the basic reaction design such as catalyts. Specifically, following a brief review on catalyst design for element strategy and sustainability, discussion is directed to: strategies for precision sequence control in synthetic (carbon-chain based) macromolecules; tandem catalysis in copolymerization towards one-pot gradient copolymers; and core-functionalized star polymers for nano-reaction space and host-guest recognition. The article’s messages include that living radical polymerization has now led to the preparation of well-defined macromolecules within the reach of researchers beyond polymer chemistry; and that we may now achieve precise structural control and advanced functions as seen in nature, such as DNA, peptide, and enzyme. |
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