New Materials based on Organosilicon Chemistry

基于有机硅化学的新材料

• 批准号: 09044101
• 负责人: SAKURAI Hideki
• 金额: $ 4.42万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B).
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1999
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09044101/
• 关键词: Polysilane; Micelle; Block Copolymer; Cross-Linking; Self-Assembly; Nano-Organized System; Silyene; Disilene; 環化反応; ジシレン; 反応性中間体; ブロック共重合体; マスクしたジシレン; アニオン重合; 高分子ミセル; 臨界ミセル濃度; シロール; σ共役

We report the formation of self-assembled micelles and shell-cross-linked micelles of amphiphilic polysilane block copolymers. Poly(1, 1-dimethyl-2, 2-dihexyldisilene)-b-poly-(methacrylic acid) (PMHS-b-PMAA) were prepared by sequential anionic polymerization of masked disilenes and then with trimethylsilyl methacrylate, followed by hydrolysis of the trimethylsilyl protecting group. PMHS-b-PMAA is soluble but obviously self-assembled in water to form polymer micelles. Since PMHS-b-PMAA has a reactive methacrylic acid block, a shell cross-linking reaction of the polymer micelles was examined to form shell-cross-linked micelles (SCM). Encapsulating and release of guest molecules for the nano-organization system were examined. In this system, the polysilane core is surrounded by a partially cross-linked shell of poly(methacrylic acid). Since the polysilane core part can undergo photochemical degradation, it is expected to provide hollow sphere particles (hollow shell cross-linked micelles, HSCM) by a photochemical process. The synthesis of nanometer-sized hollow particles derived from polysilane shell cross-linked micelles and demonstrates their macromolecular architectures that undergo reversible uptake of guest molecules are also examined.Next, we report the intramolecular dimerization of remotely generated silylenes in a molecule. Alpha, omega-bissilylene, such as 1, 6-disilahexane-1, 1, 6, 6-tetrayl, generated at low temperature undergo efficient intermolecular dimerization to give cyclic disilenes, 1, 2-disilacyclohexene-1. Cyclic disilenes are trapped by alcohols or 2, 3-dimethylbutadiene.

我们报道了两亲性聚硅烷嵌段共聚物自组装胶束和壳交联胶束的形成。采用阴离子聚合法合成了聚（1，1-二甲基-2，2-二己基二硅烯）-b-聚甲基丙烯酸（PMHS-b-PMAA）。PMHS-b-PMAA是可溶的，但在水中明显自组装形成聚合物胶束。由于PMHS-b-PMAA具有反应性甲基丙烯酸嵌段，因此检查聚合物胶束的壳交联反应以形成壳交联胶束（SCM）。考察了客体分子在纳米结构体系中的包封和释放。在该体系中，聚硅烷核被部分交联的聚（甲基丙烯酸）壳包围。由于聚硅烷核部分可以经历光化学降解，因此期望通过光化学过程提供中空球颗粒（中空壳交联胶束，HSCM）。纳米尺寸的空心粒子的合成来自聚硅烷壳交联胶束，并展示了他们的大分子结构，进行可逆摄取的客体分子也examined.Next，我们报告的分子内二聚远程生成的亚甲硅烷基在一个分子。在低温下生成的α，ω-双亚甲硅烷基，如1，6-二硅杂己烷-1，1，6，6-四基，进行有效的分子间二聚反应，得到环状二亚甲硅烷基，1，2-二硅杂环己烯-1。环状二硅烯被醇或2，3-二甲基丁二烯捕获。

项目成果

T.Sanji, M.Iwata, M.Watanabe, T.Hoshi, and H.Sakurai: "Highly Selective Mono- and Polyallylation of Polychlorosilanes and Disilanes"Organometallics. 17. 5068-5071 (1998)

T.Sanji、M.Iwata、M.Watanabe、T.Hoshi 和 H.Sakurai：“多氯硅烷和乙硅烷的高度选择性单烯丙基化和多烯丙基化”有机金属化合物。

T.Hoshi, H.Yasuda, T.Sanji, and H.Sakurai: "Synthesis of Disilacycloalkenes by Ruthenium Catalyzed Ring-Closing Metathesis (RCM) Reaction of α, ω-Bis(allyldimethylsilyl)-Substituted Compounds"Bull.Chem.Soc.Jpn.. 72. 821-827 (1999)

T.Hoshi、H.Yasuda、T.Sanji 和 H.Sakurai：“通过钌催化的 α, ω-双（烯丙基二甲基甲硅烷基）取代化合物的闭环复分解 (RCM) 反应合成二硅杂环烯烃”Bull.Chem.Soc .日本..72.821-827 (1999)

T.Hoshi: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene" Chem.Lett. 427-428 (1998)

T.Hoshi：“三甲基甲硅烷基甲基取代的掩蔽二硅烯的分子结构和光化学反应”Chem.Lett。

T.Hoshi: "Synthesis of Disilacycloalkenes by Ruthenium Catalyzed Ring-Closing Metathesis (RCM) Reaction of α,ω-Bis(allyldimethylsilyl)-Substituted Compounds"Bull.Chem.Soc.Jpn.. 72. 821-827 (1999)

T.Hoshi：“通过钌催化的 α,ω-双(烯丙基二甲基甲硅烷基)-取代化合物的闭环复分解 (RCM) 反应合成二硅杂环烯烃”Bull.Chem.Soc.Jpn.. 72. 821-827 (1999)

T. Sanji: "Self-Assembled Micelles of Amphiphilic Polysilane Block Copolymers"Macromolecules. 32. 5718-5720 (1999)

T. Sanji：“两亲性聚硅烷嵌段共聚物的自组装胶束”大分子。