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New Materials based on Organosilicon Chemistry

Research Project

Project/Area Number 09044101
Research Category

Grant-in-Aid for Scientific Research (B).

Allocation TypeSingle-year Grants
Section一般
Research Field Inorganic chemistry
Research InstitutionScience University of Tokyo

Principal Investigator

SAKURAI Hideki  Faculty of Science and Technology, Science University of Tokyo Prof., 理工学部, 教授 (70025873)

Co-Investigator(Kenkyū-buntansha) 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
Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
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)
KeywordsPolysilane / 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
Research Abstract

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.

Report

(4 results)
  • 1999 Annual Research Report   Final Research Report Summary
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (35 results)

All Other

All Publications (35 results)

  • [Publications] T. Sanji: "Encapsulation of Polysilane into Shell Cross-Linked Micelles"Chem. Commun.. 2201-2202 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Sanji: "Self-Assembled Micelles of Amphiphilic Polysilane Block Copolymers"Macromolecules. 32. 5718-5720 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Sanji: "A Statistical Model for the Cooperative Thermochromic Transition of Polysilanes"Macromolecules. 32. 3788-3794 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Sanji: "Silole-Incorporated Polysilanes"J. Am. Chem. Soc.. 120. 4552-4553 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T. Sanji: "Anionic Ring Opening Polymerization of Octamethyltetrasilacyclopentane"Chem. Lett.. 1121-1122 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Sakurai: "The Chemistry of Organic Silicon Compounds"J. Wiley & Sons,. 27 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H. Sakurai: "Macromolecular Design of Polymeric Materials"Marcel Dekker, Inc.. 16 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji, Y.Nakatsuka, F.Kitayama, and H.Sakurai: "Encapsulation of Polysilane into Shell Cross-Linked Micelles"Chem.Commun.. 2201-2202 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji, F.Kitayama, and H.Sakurai: "Self-Assembled Micelles of Amphiphilic Polysilane Block Copolymers"Macromolecules. 32. 5718-5720 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji, M.Funaya, and H.Sakurai: "Anionic Polymerization of Tetraphenylgermole-spiro-cyclogermatetrasilane, A Striking Contrast in the Mechanism to the Corresponding Silole Case"Chem.Lett.. 547-548 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji, K.Sakamoto, H.Sakurai, and K.Ono: "A Statistical Model for the Cooperative Thermochromic Transition of Polysilanes"Macromolecules. 32. 3788-3794 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 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)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji, T.Sakai, C.Kabuto, and H.Sakurai: "Silole-Incorporated Polysilanes"J.Am.Chem.Soc.. 120. 4552-4553 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji, K.Sakamoto, and H.Sakurai: "Kinetics of Chain Organization at the Thermochromic Transition of Polysilanes"Chem.Lett.. 255-256 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Hoshi, R.Shimada, C.Kabuto, T.Sanji, and H.Sakurai: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene"Chem.Lett.. 427-428 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] H.Sakurai, T.Sanji, T.Sakai, and H.Hanao: "Anionic Polymerization of Silicon-Containing Rings"Phosphorus, Sulfur, and Silicon. 124. 173 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji, H.Hanao, and H.Sakurai: "Anionic Ring Opening Polymerization of Octamethyltetrasila-cyclopentane"Chem.Lett.. 1121-1122 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] T.Sanji: "Encapsulation of Polysilane into Shell Cross-Linked Micelles"Chem.Commun.. 2201-2202 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Sanji: "Self-Assembled Micelles of Amphiphilic Polysilane Block Copolymers"Macromolecules. 32. 5718-5720 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Sanji: "Anionic Polymerization of Tetraphenylgemole-spiro-cyclogermatetrasilane,A Striking Contrast in the Mechanism to the Correponding Silole Case"Chem.Lett.. 547-548 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Sanji: "A Statistical of Disilacycloalkenes by Ruthenium Catalyzed Ring-Closing Metathesis (RCM) Reaction of α,ω-Bis(allyldimethylsilyl)-Substitued Compounds"Bull.Chem.Soc.Jpn.. 72. 821-827 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Hoshi: "Synthesis of Disilacycloalkenes by Ruthenium Catalyzed Ring-Closing Metathesis (RCM) α,ω-Bis(allyldimethylsilyl)-Substituted Compounds"Bull. Chem. Soc. Jpn.. 72. 821-827 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] T.Sanji: "Highly Selective Mono-and Polyallylation of Polychlorosilanes and Disilanes" Organometallics. 17. 5068-5071 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Sanji: "Silole-Incorporated Polysilanes" J.Am.Chem.Soc.120. 4552-4553 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Hoshi: "Synthesis of Disilacycloalkenes by Ruthenium Catalyzed Ring-Closing Metathesis(RCM)Reaction of a,w-Bis(allydimethylsilyl)-Substituted Compounds" Bull.Chem.Soc.Jpn.72. in press (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Hoshi: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene" Chem.Lett.427-428 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Iwamoto: "Bimolecular Reactions of Tetrakis(tr alkylsilyl)disilenes with Various Reagents" Bull.Chem.Soc.Jpn.71. 2741-2747 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] E.Ebata: "Planar Hexsasilylbenzene diaanion with thermally accessible triplet state" J.Am.Chem.Soc.120. 1335-1336 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Sakurai: "The Chemistry of Organic Silicon Compounds" John Wiley & Sons Ltd, 28 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Sanji: "Anionic Ring Opening Polymerization of Octamethyltetrasilacyclopentane" Chem.Lett.1121-1122 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Sanji: "Kinetics of Chain Organization at the Thermochromic Transition of Polysilanes" Chem.Lett.255-256 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Sakurai: "Anionic Polymerization of Silicon-Containing Rings" Phosphorus,Sulfur,and Silicon. in press.

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Sakurai: "John Wiley & Sons" Mechanism and structures in alcohol addition reactions of disilenes and silenes(in press),

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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