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Synthesis and Polymerization Behavior of New Monomers based on Highly Conjugated Quinoid Structure

Research Project

Project/Area Number 09650978
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子合成
Research InstitutionMIE UNIVERSITY

Principal Investigator

ITOH Takahiro  Mie Univ., Dept of Chem. for Materials, Professor, 工学部, 教授 (90126954)

Project Period (FY) 1997 – 1999
Project Status Completed (Fiscal Year 1999)
Budget Amount *help
¥3,400,000 (Direct Cost: ¥3,400,000)
Fiscal Year 1999: ¥1,000,000 (Direct Cost: ¥1,000,000)
Fiscal Year 1998: ¥1,600,000 (Direct Cost: ¥1,600,000)
Fiscal Year 1997: ¥800,000 (Direct Cost: ¥800,000)
KeywordsQuinodimethane / Quinone Methide / Alternating Copolymerization / Equilibrium Polymerization / Terpolymerization / Aromatic Bisketene / Quinonoid Compounds / Polymerizability / 重合機構 / ヘテロキノジメタン / 固相重合 / 芳香族ビスケテン化合物 / 置換キノジメタン化合物 / 立体効果 / 共重合様式変化
Research Abstract

7-Alkoxycarbonyl-7,8,8-tricyanoquinodimethanes, 7,7-bis (alkoxycarbonyl), 8,8-dicyanoquinodimethanes, and 7,8-bis (benzyloxycarbonyl)-7,8 cicyanoquinodimethane were synthesized successfully as isolable crystals at room temperature. 7,7 Bis (alkoxycarbonyl)-8,8-dicyanoquinodimethane with meldrum acid unit at the exocyclic position had same electron-accepting property to 7,7,8,8-tetracyanoquinodimethane and copolymerized with styrene in an alternating fashion. Homopolymer of 7,8-bis (benzyloxycarbonyl)-7,8-cicyanoquinodimethane was photodegaradable due to existence of phenyl groups.
7-Alkoxycarbonyl-7-cicyanobenzoquinone methides and 7-cyano-7(phenyl)benzoquinone methide were synthesized successfully as isolate crystals at room temperature. It was concluded that polymerizability of 7-Alkoxycarbonyl-7-cicyanobenzoquinone methides depends significantly on the steric effect of the alkoxy groups. Spontaneous polymerization mechanism of 7-cyano-7-(phenyl)benzoquinone with styrene could be explained well by both diradical intermediate formation in the initiation step by the bond-forming initiation mechanism and chain addition like a conventional radical copolymerization in the propagation step.
1,4-Dicarbonyl-1,4-dihydronaphthalene generated in situ in a degassed benzene copolymerized with benzoquinones and benzoquinone diimines spontaneously and alternatingly to give aromatic polyesters and polyamides, respectively.
2,5-Bis(dicyanomethylene)-2,5-dihydrofuran, 2,5-dimethylene-2,5-dihydrothieno[3,2-b]thiophenes, and 2,5-bis(1.3-dithiolan-2-ylidene)-2,5-dihydrothiopene were synthesized successfully as isolable crystals at room temperature. It was pointed out that polymerizability depends significantly on the energy difference between benzenoid structure and quinonoid structure. Polymerization of 2,5-Bis(1.3-dithiolan-2-ylidene)-2,5-dihydrothiophene was found to be driven by both release of ring strain energy and aromatization energy.

Report

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

    (44 results)

All Other

All Publications (44 results)

  • [Publications] Takahito Itoh e al.: "Synthesis and Polymerization of 7-Alkoxycarbonyl-7, 8, 8-tricyanoquinodimetbanes and 7, 7-Bis(alkoxycarbonyl)-8, 8-dicyanoquinodimethanes"Tetrahedron. 53. 15247-15261 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Polymerization Behavior of Electron-Accepting Substituted Quinodimethanes"Macromolecular Chemistry and Physics. 198. 1997-2016 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Equilibrium Polymerization of 7-Alkoxycarbonyl-7-cyano-1, 4-benzoquinone Methides, Substituent Effect on Polymerizability, and Copolymerization with Styrene"Macromolecules. 31. 1501-1507 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Synthesis of Aromatic Polyesters and Polyamide by Alternating Copolymerization of 1, 4-Dicarbonyl-1, 4-dihydronaphthalene with Benzoquinones and Benzoquinone Diimines"Journal fof Polymer Science : Part A : Polymer Chemistry. 36. 1929-1936 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Polymerization Behavior of 2, 5-Bis(dicyanomethylene)-2, 5-dihydrofuran"Journal fof Polymer Science : Part A : Polymer Chemistry. 37. 1285-1292 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Synthesis and Polymerization of 2, 5-Dimethylene-2,5-dihydrothieno[3, 2-b]thiophene Derivatives : The Structure and Reactivity of Quinonoid Monomers"Journal fof Polymer Science : Part A : Polymer Chemistry. 37. 3027-3039 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Synthesis of 7, 8-Bis(benzyloxycarbonyl)-7, 8-dicyanoquinodimethanes, Polymerization, and Some Properties of its Polymer"Designed Monomers and Polymers. 2. 311-324 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Synthesis of 2, 5-Bis(1, 3-dithiolan-2-ylidene)-2, 5-dihydrothiophene and its Novel Polymerization in the Presence of Oxygen"Macromolecules. 32. 1308-1311 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh e al.: "Synthesis and Polymerization Behavior of 7-Cyano-7-(phenyl)benzoquinone Methide"Macromolecules. 33. 269-277 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh et al.: "Recent Research Development in Polymer Science Vol.2, Part 1 "Polymerization of Quinonoid Monopmers"(分担執筆)"Transworld Research Network. 18 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 伊藤敬人: "ラジカル重合ハンドブック「第7章 第3節 キシリトン型モノマー」"エス・ティー・エヌ(分担執筆). 5 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] 伊藤敬人: "高分子 テトラキス(アルコキシカルボニル)キノジメタン類の固相重合(解説記事)"高分子学会. 1 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Synthesis and Polymerization of 7-Alkoxycarbonyl-7,8,8-tri-cyanoquinodimethanes and 7,7-Bis(alkoxycarbonyl)-8,8-Dicyanoquinodimethanes"Tetrahedron. 53. 15247-15261 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Polymerization Behavior of Electron-Accepting Substituted Quinodimethanes"Macromolecular Chemistry and Physics. 198. 1997-2016 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Equilibrium Polymerization of 7-Alkoxycarbonyl-7-cyano-1,4-benzoquinone Methides, Substituent Effect on Polymerizability, and Copolymerizations with Styrene"Macromolecules. 31. 1501-1507 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Synthesis of Aromatic Polyesters and Polyamides by Alternating Copolymerization of 1,4-Dicarbonyl-1,4-dihydronaphthalene With Benzoquinones and Benzoquinone Diimines"J. Polym. Sci. Part A : Polym Chem.. 36. 1929-1936 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Polymerization Behavior of 2,5-Bis(dicyanomethylene)-2,5-Dihydrofuran"J. Polym. Sci. Part A : Polym Chem.. 37. 1285-1292 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Synthesis and Polymerization of 2,5-Dimethylene-2,5-dihydrothieno[3,2-b]thiophenes Derivatives ; The Structure and Reactivity of Quononoid Monomers"J. Polym. Sci. Part A : Polym Chem.. 37. 3027-3039 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Synthesis of 7,8 Bis(benzyloxycarbonyl)-7,8-dicyanoquinodimethanes, Polymerization in the Presence of Oxygen"Designed Monomers and Polymers. 2. 311-324 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Synthesis of 2,5-Bis(1.3-dithiolan-2-ylidene)-2,5-dihydrothiopene and its Novel Polymerization in the Presence of Oxygen"Macromolecules. 32. 1308-1311 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Synthesis and Polymerization Behavior of 7-Cyano-7-(phenyl)-Benzoquinone Methide"Macromolecules. 33. 269-277 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "Polymerization of Quinonoid Monomers"Transworld Research Network. 18 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahiro Itoh et al.: "NTS"Xylylene Type Monomers. 5 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1999 Final Research Report Summary
  • [Publications] Takahito Itoh et al.: "Synthesis and Polymerization of 7-Alkoxycarbonyl-7,8,8-tricyanoquinodimethanes and 7,7-Bis(alkoxycarbonyl)-8,8-dicyanoquinodimethanes"Tetrahedron. 53. 15247-15261 (1997)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Polymerization Behavior of Electron-Accepting Substituted Quinodimethanes"Macromolecular Chemistry and Physics. 198. 1997-2016 (1997)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Equilibrium Polymerization of 7-Alkoxycarbonyl-7-cyano-1,4-benzoquinone Methides,Substituent Effect on Polymerizability,and Copolymerizations with Styrene"Macromolecules. 31. 1501-1507 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Synthesis of Aromatic Polyesters and Polyamides by Alternating Copolymerization of 1,4-Dicarbonyl-1,4-dihydronaphthalene with Benzoquinones and Benzoquinone Diimines"Journal of Polymer Science.Part A: Polymer Chemistry. 36. 1929-1936 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Polymerization Behavior of 2,5-Bis(dicyanomethylene)-2,5-dihydrofuran"Journal of Polymer Science.Part A: Polymer Chemistry. 37. 1285-1292 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Synthesis and Polymerization of 2,5-Dimethylene-2,5-dihydrothieno[3,2-b]thiophene Derivatives : The Structure and Reactivity of Quinonoid Monomers"Journal of Polymer Science.Part A: Polymer Chemistry. 37. 3027-3039 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Synthesis of 7,8-Bis(benzyloxycarbonyl)-7,8-dicyanoquinodimethanes,Polymerization,and Some Properties of its Polymer"Designed Monomers and Polymers. 2. 311-324 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Synthesis of 2,5-Bis(1,3-dithiolan-2-ylidene)-2,5-dihydrothiophene and its Novel Polymerization in the Presence of Oxygen"Macromolecules. 32. 1308-1311 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Synthesis and Polymerization Behavior of 7-Cyano-7(phenyl)benzoquinone Methide"Macromolecules. 33. 269-277 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et al.: "Recent Research Developments in Polymer Science Vol.2 Part I "Polymerizations of Quinonoid Monomers"(分担執筆)"Transworld Research Network. 18 (1998)

    • Related Report
      1999 Annual Research Report
  • [Publications] 伊藤 敬人: "ラジカル重合ハンドブック 「第7章 第3節 キシリレン型モノマー」 (分担執筆)"エヌ・テイー・エス. 5 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] 伊藤 敬人: "高分子 「テトラキス(アルコキシカルボニル)キノジメタン類の固相重合」 (解説記事)"高分子学会. 1 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Takahito Itoh et.al.: "Synthesis and Polymerization of 7-Alkoxycarbonyl-7,8,8-tricyanoquinodimethanes and 7,7-Bis(alkoxycarbonyl)-8,8-dicvanoquinodimethanes" Tetrahedron. 53. 15247-15261 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takahito Itoh et.al.: "Polymerization behavior of electron-accepting substituted quinodimethanes" Macromolecular Chemistry and Physics. 198. 1997-2016 (1997)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takahito Itoh et.al.: "Equilibrium Polymerization of 7-Alkoxycarbonyl-7-cyano-1,4-benzoquinone Methides,Substituent Effect on Polymerizability and Copolymerizations with Styrene Polymerization" Macromolecules. 31. 1501-1507 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takahito Itoh et.al.: "Synthesis of Aromatic Polyesters and Polyamides by Alternating Copolymerizations of 1,4-Dicarbonyl-1,4-dihydronaphthalene with Benzoquinones and Benzoquinone Diimines" Journal of Polymer Science,Part A:Polymer Chemistry. 36. 1929-1936 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takahito Itoh et.al.: "Polymerization Behavior of 2,5-Bis(dicyanomethylene)-2,5-dihydrofuran" Journal of Polymer Science,Part A:Polymer chemistry. (in press).

    • Related Report
      1998 Annual Research Report
  • [Publications] Takahito Itoh et.al.: "Synthesis of 2.5-Bis(1,3-dithiolan-2-ylidene)-2,5-dihydrothiophene and Its Novel Polymerization in the Presence of Oxygen" Macromolecules. (in press).

    • Related Report
      1998 Annual Research Report
  • [Publications] Takahito Itoh et.al.: "Recent Research Developments in Polymer Science Vol.2 Part I(分担)" Transworld Research Network, 18 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Takahito Itoh 他: "Synthesis and Polymerization of 7-Alkoxycarbonyl-7, 8, 8-tricyanoquinodimethanes and 7, 7-Bis (alkoxycarbonyl) -8, 8-dicyanoquinodimethanes" Tetrahedron. vol.53. 15247-15261 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Takahito Itoh 他: "Equilibrium Polymerization of 7-Alkoxycarbonyl-7-cyano-1, 4-benzoquinone Methides, Substituent Effect on Polymerizability, and Copolymerization with Styrene" Macromoleculs. (in press).

    • Related Report
      1997 Annual Research Report

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

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