| 高分子 Vol.62 No.5 |
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特集
精密聚合的开发与实际应用 |
| 展望 |
| 通过FI催化剂制备的烯烃聚合物的结构控制与功能性材料中的应用 | 三谷 诚, 藤田照典 |
| <Abstract>
三井化学公司开发的“茂后”烯烃聚合催化剂,即“FI催化剂”不仅具有很高的催化活性,还可以实现以往极其困难的烯烃聚合物的精密结构控制.该公司利用了FI催化剂开发了多种具有独特的特性的功能性烯烃聚合物. Keywords: Olefin Polymerization / Postmetallocene Catalysts / FI Catalysts / Polyolefins |
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| 活性阳离子聚合法在功能性材料制备中的应用 | 青岛贞人, 金泽有纩 |
| <Abstract>
近几年未来型的功能性材料如雨后春笋般相继问世,但利用阳离子聚合的研究例子相对甚少.如今终于有了一些进展,利用阳离子聚合的功能性材料的研究获得了强大的推进力.本文概述了最近这些方面的研究例子,并对今后的可能性进行了阐述. Keywords: Cationic Polymerization / Living Polymerization / Functional Polymer / Stimuli-Responsive Polymer / Thermosensitive Polymer |
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| 利用催化剂转移型缩聚反应的π共轭聚合物的精密合成 | 野嶋雅贵,太田佳宏,横泽勉 |
| <Abstract>
π共轭聚合物是现在最为引人注目的有机电子材料之一,但一般都是通过缩聚反应来合成制备的,故控制其分子量及终端结构是非常困难的. 催化剂转移型缩聚反应(CTCP)是实现这种精密控制的有效途径.本文对CTCP的开发及其普遍性和最新进展进行了介绍. Keywords: π-Conjugated Polymer / Catalyst-Transfer Condensation Polymerization |
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| 话题 |
| 新型烃类单体的阴离子活性聚合 | 石曾根 隆 |
| <Abstract>
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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| 通过S乙烯基单体活性自由基聚合法的功能性高分子的精密合成 | 森 秀晴 |
| <Abstract> 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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| 通过活性阳离子聚合法的聚异丁烯的开发与实用化研究 | 山中祥道,木村胜彦 |
| <Abstract> 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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| 通过阴离子活性聚合的细微加工定向自组装技术的开发 | 山口佳一 |
| <Abstract> 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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| 氮氧稳定基为基础的活性自由基聚合的开发与应用 | 有浦芙美 |
| <Abstract> 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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| 高分子科学与我: 个人独白 |
| 探索化学! | 小门宪太 |
| <Abstract> “享受化学!”是我的导师Prof. Chujo的口头禅. 本文描述了我个人在探索化学的路途中的一些点点滴滴. |
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| 高分子科学最新进展 |
| 精密自由基聚合的进展: 反应控制与功能性分子链的精密设计 | 大内 诚, 寺岛崇矢, 泽本光男 |
| <Abstract>
本文聚焦了金属介导精密活性自由基聚合研究中一些尖端课题的最新进展。尤其对催化剂的设计从元素的普遍性和可持续性的角度进行了综述，主要围绕着合成大分子（碳碳链）的精密控制方法论，梯度共聚物的串联催化共聚及星形聚合物的纳米反应空间和主客体识别核心功能进行了讨论。本文向读者们传递活性自由基聚合在精密大分子制备中的超乎以往传统高分子化学理论的极佳利便性，以及在精密结构控制和DNA，肽，酶等自然界生物高分子中的应用等。 Keywords: Living Radical Polymerization / Catalyst / Element Strategy / Sequence / Template / Tandem Catalysis / Gradient Copolymer / Star Polymer |
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