高分子　Vol.68　No.2　2019年2月

高分子　Vol.68　No.2

特集　匠が拓く高分子合成の新しい技

展望　COVER STORY: Highlight Reviews

二核遷移金属錯体に基づく重合触媒の設計
Design of Polymerization Catalysts Based on Dinuclear Transition Metal Complexes

竹内　大介
Daisuke TAKEUCHI

＜要旨＞二核遷移金属錯体は、しばしば単核錯体に比べて高いオレフィン重合触媒活性を示し、より高分子量のポリマーを与える。近年、金属中心が近接した位置に固定された二核錯体や異種金属二核錯体が設計され、それにより単核錯体では困難だった重合も可能になっている。本稿では、オレフィン重合を中心に、最近の二核遷移金属錯体触媒の例を紹介する。
Keywords: Metal-Catalyzed Polymerization / Dinuclear Catalyst / Transition Metal Catalyst / Olefin Polymerization / Copolymerization / Tandem Polymerization

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C-H結合の活性化を利用した新奇重合反応
Polymer Synthesis via Metal-Catalyzed C-H Activation

西浦正芳・侯　召民
Masayoshi NISHIURA, Zhaomin HOU

＜要旨＞金属触媒を用いるC-H結合の活性化と変換反応は、原子効率に優れた新手法として有機合成の分野で数多く報告されている。その高いポテンシャルが近年高分子合成においても注目されている。本稿では、遷移金属触媒や希土類金属触媒によるC-H結合活性化反応を活用した重付加反応や連鎖移動重合などについて、最近の研究例を中心に概説する。
Keywords: Rare Earth Metal / Ruthenium / C-H Polyaddition / Alternating Copolymerization / Chain Transfer Polymerization / Step-Growth Polymerization

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金属－炭素結合へのイソシアニドと不飽和炭化水素の交互挿入反応に基づく環化共重合
Cyclocopolymerization Based on Alternative Insertions of Isocyanide and Unsaturated Hydrocarbons into a Palladium-Carbon Bond

神林　直哉・鬼塚　清孝
Naoya KANBAYASHI, Kiyotaka ONITSUKA

＜要旨＞イソシアニドと異種モノマーの共重合反応は、イソシアニドの単独重合で得られるポリイソシアニドとは異なる新しい主鎖骨格を与えることから、その重合法の開発に興味がもたれる。本稿では、筆者らが最近研究している金属－炭素結合へのイソシアニドと不飽和炭化水素の交互挿入反応に基づく環化共重合反応を中心に概説する。
Keywords: Isocyanide / Organopalladium Complex / Alternative Insertion / Allene / Alkyne / Coordination Polymerization / Cyclocopolymerization / Living Polymerization

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トピックス　COVER STORY: Topics and Products

N-ヘテロ環状カルベンを開始剤とする高分子合成
Polymer Synthesis using N-Heterocyclic Carbene as the Initiator

高須　昭則
Akinori TAKASU

＜要旨＞ A diene-based cyclic polymer has been synthesized by the anionic polymerization of methyl sorbate (MS) by an N-heterocyclic carbene (NHC). Although the polymerization did not occur in toluene in the absence of any additive, quantitative monomer consumption was observed in the presence of methylaluminum bis(2,6-di-tert-butyl-4-methylphenoxide) (MAD) to afford the poly(MS) with a 1,4-trans structure, 86％ of threo diastereoselectivity, and a M_n of 23.0×10³ with narrow molecular weight distribution (M_w/M_n = 1.1₇). From the matrix assisted laser desorption/ionization (MALDI-TOF) mass spectra of poly(MS) and the hydrogenated analogue, ring-closing occurred by nucleophilic attack of the anionic propagating center into the adjacent carbon of the α-terminal imidazolimium group to afford cyclic poly(MS). In this paper, we introduced NHC-initiated ring-opning polymerization of racemic lactide to give stereoregular not cyclic but linear poly(lactide) in the presence of MAD.
Keywords: N-Heterocyclic Carbene (NHC) / Cyclic Polymer / Ring-Clossure Procedure without Highly Diluted Condition / Alkyl Sorbate / Lactide / Stereoregularity

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α-機能化アクリル酸エステルの共役置換による高分子の合成・分解・変換
Construction, Destruction, and Transformation of Polymer Main Chain by Conjugate Substitution of α-(Halomethyl)acrylates

髙坂　泰弘
Yasuhiro KOHSAKA

＜要旨＞ Conjugate substitution of α-(halomethyl)acrylates is an attractive reaction for polymerization, polymer degradation and modification, because it affords α-functionalized acrylates with quantitative yields under ambient condition. For example, bis[α-(chloromethyl)acrylate] underwent polycondensation with bisphenols, dicarboxylic acids, primary monoamines, and dithiols to yield the corresponding poly(conjugated esters). Among them, the polymers prepared from dicarboxylic acids were degradable by the treatment with thiols, as the α-(acyloxymethyl)acrylate skeletons in the backbone is also active to conjugate substitution. In a similar mechanism, the poly(ester ester) were converted to poly(ester sulfide) through the conjugate substitution with dithiols. The conversion approximately agreed with the feed ratio of dithiols against the α-(acyloxymethyl)acrylate skeletons. Since conjugate substitution proceeds under mild conditions, the reaction is compatible to other nucleophilic reactions. α-(Chloromethyl)acryloyl chloride that can accept both conjugate substitution and acyl substitution was polymerized with dicarbonyl chlorides and bisphenols, resulting in polyacylate with α-(acyloxymethyl)acrylate skeletons. The polycondensation of α-(bromomethyl)acrylate and dithiols was achieved by the combination of conjugate substitution and addition reactions.
Keywords: Conjugate Substitution / α-(Halomethyl)acrylates / Poly(conjugated ester)s / Polycondensation / Tandem Reaction / Domino Reaction / Polymer Degradation / Main Chain Transformation

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触媒設計がカギを握る次世代タイヤ材料
Catalyst Design Holds the Key to the Next-Generation Tire Materials

会田　昭二郎
Shojiro KAITA

＜要旨＞ Due to technology innovations, future direction of mobility will change significantly, such as to electric vehicles (EV)･fuel cell vehicles (FCV) and autonomous vehicles. Following this trend, demand for next generation tires will also diversify. Focusing on “long life / high strength tire”, which is one of the most important tasks for realizing the future mobility society, it is necessary to develop new high value tire materials (e.g., new rubber materials). Here, we will report the creation of two novel polymers using our “novel polymerization catalyst”, a new isoprene rubber with precise molecular structure and a polymer having rubber and resin at a molecular level for the first time.
Keywords: Polymerization Catalyst / Future Mobility / High Strength / New Rubber Materials / Isoprene Rubber / Rubber and Resin

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多成分連結反応を活用した高分子合成
Polymer Synthesis with Multi-Component Reactions

覚知　亮平
Ryohei KAKUCHI

＜要旨＞ This manuscript highlights a new stream in polymer chemistry, which is essentially taking advantage of the synthetic utility of multi-component reactions (MCRs). For example, the author has been showing the synthetic benefits of the Kabachnik-Fields (KF) reaction. The KF reaction was dicoverd in 1950s and refers to the reaction among amines, aldehydes, and phosphonates to afford the corresponding α-aminophosphonate esters. Despite the fruitful features of the KF reaction, the KF reaction had not been incorporated into polymer science until very recently. The author has merged the KF reaction as an elementary reaction in polymer science, with which facile post polymerization functionalization and a step growth polymerization were realized to access a wide range of polymeric α-aminophosphonate esters.
Keywords: Postmodification / Polycondensation / Multicomponent Reaction / Biomass

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グローイングポリマー　Polymer Science and I: A Personal Account

免疫づくり
Coping Ability Training

弓場　英司
Eiji YUBA

＜要旨＞ This essay describes the relationship between my experiences and current research topics about polymer-based immunity-inducing systems. Various occurrences in my life provided me with the coping ability to manage the research. Especially, the experience in drug eruption strongly affected me to be interested in control of immunological reactions by synthetic molecules.

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高分子科学最近の進歩　Front-Line Polymer Science

リビングアニオン重合～新規モノマーの開拓
Living Anionic Polymerization～Development of New Monomers

石曽根　隆・後関　頼太
Takashi ISHIZONE, Raita GOSEKI

＜要旨＞ The living anionic polymerization is a promising way for synthesis of well-defined polymers since discovered by Szwarc in 1956. Recently, intrigued chain-end functionalized polymers and architectural polymers such as multiblock copolymer, star-shaped polymer, and graft polymer are also synthesized precisely by taking advantage of “living” nature of the chain-end anion. Nowadays, a wide variety of monomers can be utilized for the living anionic polymerization, although there has been a limit in the anionic polymerizable monomer due to the high reactivity of the anionic species. Recent progress on the new initiator systems, suitable design of monomer structures, and effective stabilization of the propagating anion with additives enables to significantly expand the range of monomers. Those novel designed attractive monomers include divinylbenzenes, adamantane containing vinyl monomers, exomethylene monomers, functional (meth)acrylates, (meth)acrylamides, and cyclic monomers. In this review, we highlight recent advances of the living anionic polymerization, particularly recent developed monomers showing anionic polymerizability.
Keywords: Living Anionic Polymerization / Block Copolymers / Styrene Derivatives / Divinyl Benzenes / Adamantane Containing Vinyl Monomers / Exomethylene Monomers / Diene Derivatives / Polar Monomers / Cyclic Monomers

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