SANJI Takanobu Faculty of Science and Technology, Science University of Tokyo Assistant, 理工学部, 助手 (00287484)
ABE Yoshimoto Faculty of Science and Technology, Science University of Tokyo Prof., 理工学部, 教授 (20084460)
WEST Robert 米国, ウィスコンシン大学化学科, 教授
|Budget Amount *help
¥6,900,000 (Direct Cost: ¥6,900,000)
Fiscal Year 1999: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1998: ¥2,300,000 (Direct Cost: ¥2,300,000)
Fiscal Year 1997: ¥2,400,000 (Direct Cost: ¥2,400,000)
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.