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Development of New Type Polymerization Using Crystalline Media

Research Project

Project/Area Number 14550832
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子合成
Research InstitutionTokyo Institute of Technology

Principal Investigator

MASAHITO Suzuki  Tokyo Institute of Technology, Dept. of Org. & Polym. Mat., Associate Prof., 大学院・理工学研究科, 助教授 (20179253)

Project Period (FY) 2002 – 2004
Project Status Completed (Fiscal Year 2004)
Budget Amount *help
¥3,700,000 (Direct Cost: ¥3,700,000)
Fiscal Year 2004: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2003: ¥800,000 (Direct Cost: ¥800,000)
Fiscal Year 2002: ¥2,100,000 (Direct Cost: ¥2,100,000)
KeywordsSolid-State Polymerization / Polycondensation / Polyether / Saccharide / Polysaccharide / Highly Branched Polymer / Polysiloxane / フェノール樹脂 / シラノール / ジアステレオマー / アミノ酸
Research Abstract

1) The oxidative coupling polymerization of 2,6-dihydroxynaphthalene to poly(2,6-dihydroxy-1,5-naphthylene) took place by grinding with FeCl_3/6H_2O without any solvent. Using the cocrystals with amines, especially bezylamine, promoted the polymerization giving the higher molecular weight (Mn=〜10000) polymer.
2) Arene dimethanol derivatives underwent solid-state polycondensation forming polyether. Typically, grinding and heating (100℃ under a N_2 flow) the crystals of dl-1,3-bis(hydroxyphenylmethyl)benzene with powder of camphorsulfonic acid (5 mol%) produced the polymer (Mn:〜40000). Interestingly, the reaction mixture was white powdery throughout the polymerization without any change in appearance. The diastereomeric isomers showed different polymerizability in the solid-state but the same in the solution.
3) Solid-state polycondensations of natural mono-and di-saccharides took place in the presence of H_3PO_4 (5 mol%) by heating at 110℃ under a N_2 flow, giving a highly branched polysa … More ccharide (Conv. 11〜84%, Mw=1400〜19,000, Mn=1200〜3700); the reaction mixture was powdery throughout the polymerization. Interestingly, α- and β-anomers showed different polymerization behavior ; the former was polymerized more slowly, however, they gave comparable molecular weight polymers. Sugar fluorides underwent powder-to-powder polycondensation without any catalyst at 110-160℃ under vacuum, giving highly branched polysaccharides (Conv.=40〜95%, Mw=1400〜20000). The cross-polarized optical microscopic images at 110℃ indicated that the crystal shape of α-glucosyl fluoride was unchanged before and after the polymerization in spite of producing the amorphous polymer. 4) Various silanediols and disiloxanediols produced cyclic oligosiloxanes or linear polysiloxane by the treatment with acid or base catalyst without any solvent. Interestingly, the copolymerization of the silanediols that afforded the cyclic oligosilane produced high molecular weight polysiloxanes (10^4〜10^5), which was also obtained from the disiloxanediols. Less

Report

(4 results)
  • 2004 Annual Research Report   Final Research Report Summary
  • 2003 Annual Research Report
  • 2002 Annual Research Report
  • Research Products

    (10 results)

All 2006 2005 2003 Other

All Journal Article (8 results) Publications (2 results)

  • [Journal Article] Solid-state polycondensation of natural aldopentoses and 6-deoxyaldohexoses. Facile preparation of highly branched polysaccharid2006

    • Author(s)
      Atsushi Kanazawa, Masato Suzuki
    • Journal Title

      Polymer 47

      Pages: 176-183

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Solid-state polycondensation of natural aldopentoses and 6-deoxyaldohexoses. Facile preparation of highly branched polysaccharide2006

    • Author(s)
      Atsushi Kanazawa, Masato Suzuki
    • Journal Title

      Polymer 47

      Pages: 176-183

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Powder-to-powder polycondensation of natural saccharides. Facile preparation of highly branched polysaccharides2005

    • Author(s)
      Atsushi Kanazawa, Shohei Okumura, Masato Suzuki
    • Journal Title

      Organic and Biomolecular Chemistry 3

      Pages: 1746-1750

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] IR Spectroscopic Study on Differences between Diastereoisomeric Monomers in Solvent-Free Polycondensation2005

    • Author(s)
      Masato Suzuki, Takeshi Sasaki, Go Matsuura
    • Journal Title

      Polymer Bulletin 54

      Pages: 243-249

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Novel Solid-Statc Polymerization of Crystalline Monomer. Dehydrative Polycondensation of 1,3-Bis(hydroxyphenylmethyl)benzene2003

    • Author(s)
      Takeshi Sasaki, Kazuyuki Hayashibara, Masato Suzuki
    • Journal Title

      Macromolecules 36

      Pages: 279-281

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Solvent-Free Polycondensation of 1,3-Bis(hydroxyphenylmethyl)benzene. II. The Dramatic Difference in the Polymerization Behavior between Meso and Racemic Isomers2003

    • Author(s)
      Masato Suzuki, Takeshi Sasaki, Go Matsuura, Mika Kimura
    • Journal Title

      Journal of Polymer. Science, Part A, Polymer. Chemistry 41

      Pages: 3564-3571

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Novel Solid-State Polymerization of Crystalline Monomer. Dehydrative Polycondensation of 1,3-Bis(hydroxyphenylmethyl)benzene2003

    • Author(s)
      Takeshi Sasaki, Kazuyuki Hayashibara, Masato Suzuki
    • Journal Title

      Macromolecules 36, 37

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Journal Article] Solvent-Free Polycondensation of 1,3-Bis(hydroxyphenylmethyl)benzene. II. The Dramatic Difference in the Polymerization. Behavior between Meso and Racemic Isomers2003

    • Author(s)
      Masato Suzuki, Takeshi Sasaki, Go Matsuura, Mika Kimura
    • Journal Title

      Journal of Polymer.Science, Part A, Polymer.Chemistry.(Special Issue : Japan-US Seminar on Advanced Polymer Chemistry for the 21st Century) 41

      Pages: 3564-3571

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2004 Final Research Report Summary
  • [Publications] MASATO SUZUKI, TAKESHI SASAKI, GO MATSUURA, MIKA KIMURA: "Solvent-Free Polycondensation of 1,3-Bis(hydroxyphenylmethyl)benzene. II. The Dramatic Difference in the Polymerization Behavior between Meso and Racemic Isomers"Journal of Polymer Science : Part A : Polymer Chemistry. 41. 3564-3571 (2003)

    • Related Report
      2003 Annual Research Report
  • [Publications] T.Sasaki, K.Hayashibara, M.Suzuki: "Novel Solid-State Polymerization of Crystalline Monomer Dehydrative Polymerization of 1,3-Bis(Hydroxyphenybnethyl)benzene"Macromolecules. 36・2. 279-281 (2003)

    • Related Report
      2002 Annual Research Report

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Published: 2002-04-01   Modified: 2016-04-21  

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