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Molecular Aspects of Mesophase Formation of Polymer Liquid Crystals As Revealed by ^2H NMR Analyzes and PVT Measurements

Research Project

Project/Area Number 07405045
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field 高分子構造・物性(含繊維)
Research InstitutionTokyo Institute of Polytechnics

Principal Investigator

ABE Akihiro  Tokyo Institute of Polytechnics Department of Industrial Chemistry Professor, 工学部, 教授 (50114848)

Co-Investigator(Kenkyū-buntansha) HIRAOKA Kazuyuki  Tokyo Institute of Polytechnics Department of Industrial Chemistry Lecturer, 工学部, 講師 (50267530)
UEMATSU Yoshiko  Tokyo Institute of Polytechnics Department of Industrial Chemistry Professor, 工学部, 教授 (80064260)
IMAI Yoshio  Tokyo Institute of Technlogy Department of Organic Materials Professor (50016557)
Project Period (FY) 1995 – 1996
Project Status Completed (Fiscal Year 1996)
Budget Amount *help
¥25,200,000 (Direct Cost: ¥25,200,000)
Fiscal Year 1996: ¥2,200,000 (Direct Cost: ¥2,200,000)
Fiscal Year 1995: ¥23,000,000 (Direct Cost: ¥23,000,000)
Keywordsmainchain liquid crystals / order-disorder transition / PVT properties / spacer conformation / conformational entropy / phase diagrams for binary mixtures / constant volume transition entropy / chiral spacers / エーテル型液晶 / カーボネート型液晶
Research Abstract

Our interest is to study the conformation and the thermodynamic role of flexible chains involved in an anisotropic environment. Mainchain-type liquid crystals (LC) involve flexible segments as a unit connecting two mesogenic cores. From the accumulated experimental data, transition entropies of such LCs at the nematic-isotropic interphase remain nearly invariant when divided by the number of spacers. Our study thus started from dimer and trimer model compounds having a spacer such as -O (CH_2)_nO- with n=9 and 10. These LCs can be synthesized with a precise constitution. Binary mixtures of these LCs allow us to investigate the effect of molecular weight distribution. The results of our research, supported by the Monbusho grant for a two-year period, are summarized as follows :
1. The ^2H NMR analysis provided a technique to elucidate the orientational order parameter of the individual components of a given mixture. When dimer or timer LCs were dissolved in a monomer LC,the order paramet … More er of the mosogenic units of the former were found to be lower than those of the monomeric LC.In the mainchain-type LCs, bond angles conneting the mosogenic units to the spacer play an important role in determining the orientational order of the mosogenic core.
2. The equation of state analysis (Flory's expression) indicated that the free volumes of the dimer and trimer LCs are about 20% of the core volume in the isotropic state just above the NI transition point. The volume changes at the NI transition were found to be about 10-20%.
3. Combined use of the ^2H NMR and PVT measurements revealed that variation of the spacer conformation is largely responsible for the latent entropy at the NI as well as CN transitions. This observation immediately suggests that the stereochemical constitution of the spacer involved in the mainchain LCs effectively determines various thermodynamic properties of the system. Along this line, computer design of chiral-spacers is in progress in our laboratory. Some of them have been synthesized and tested. Less

Report

(3 results)
  • 1996 Annual Research Report   Final Research Report Summary
  • 1995 Annual Research Report
  • Research Products

    (24 results)

All Other

All Publications (24 results)

  • [Publications] A.Abe: "PVT Studies on Dimer Liquid Crystals and Estimation of Transition Entropies at Constant Volume" Macromolecules. 28. 90-95 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe: "Calculation of the Conformation Entropy of Dimer Liquid Crystals and Comparison with the Observed Transition Entropies at Constant Volume" Macromolecules. 28. 96-103 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe: "Thermodynamics and Molecular Ordering of Carbonate-type Dimer Liquid Crystals with Emphasis on the Geometrical Characteristics of the Linking Group" Acta Polymer.46. 437-444 (1995)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Maeda: "High Pressure Differential Themal Analysis of Dimer Liquid Grystals : α,ω-Bis[(4,4′-cyanobiphenylyl) ox ylalkanes" Liquid Crysyals. 21. 365-371 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe: "Spatial Configuration of Chain Molecules Incorporated in Liquid Crystals and Thermodynamic Significance" Makromol.Symp.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe: "Gas Phase NMR and ab Initio Molecul ar Orbital Calculations of 5-Methoxy-1,3-dioxanes : A Critical Survey on the Gauche Effect" J.Mol.Struct.(in press).

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe and S.-Y.Nam: "PVT Studies on Dimer Liquid Crystals and Estimation of Transition Entropies at Constant Volume" Macromolecules. 28. 90-95 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe, H.Furuya, R.N.Shimizu, and S.-Y.Nam: "Calculation of the Conformation Entropy of Dimer Liquid Crystals and Comparison with the Obseved Transition Entropies at Constant Volume" Macromolecules. 28. 96-103 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] H.Furuya, S.Okamoto, A.Abe, G.Petekidis, and G.Fitas: "Dipole Moment and Optical Anisotropy Studies of Mesogenic Twin Compounds, alpha, omega-Bis [(4,4'-cyanobiphenyl)oxy] alkanes" J.Phys.Chem.99. 6483-6486 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe, H.Furuya, S.-Y.Nam, and S.Okamoto: "Thermodynamics and Molecular Ordering of Carbonate-type Dimer Liquid Crystals with Emphasis on the Geomtrical Characteristics of the Linking Group" Acta Polymer.46. 437-444 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Maeda, H.Furuya, and A.Abe: "High Pressure Differential Themal Analysis of Dimer Liquid Crystals : alpha, omega-Bis[(4,4'-cy an obiphenylyl)oxy]alkanes" Liquid Crysyals. 21. 365-371 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe: "S patial Configuration of Chain Molecules Incorporatedin Liquid Crystals and Thermodynamic Significance" Makromol.Symp.(in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] S.Okamoto, H.Furuya, and A.Abe: "Conformational Analysis of alpha-Helical Polypeptides in Two Opposite Serew Forms : A Combined Use of ^2H NMR and MD Simulation" Polym.J.27. 746-756 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe, H.Furuya, and S.Okamoto: "Conformational Transitions and Incidental Reorganization of Mesophase Structures Peculiar to Polyaspartates-A Highly Versatile System Designed by Nature" Polymer Science, Ser.A.38. 317-323 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] J.Lin, A.Abe, H.Furuya, and S.Okamoto: "Liquid Crystal Formation Coupled with the Coil-Helix Transition in the Temary System Poly (gamma-benzyl L-gulutamate)/Dichloroacetic Acid/Dichloroethane" Macromolecules. 29. 2584-2589 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe, N.Ichimura, T.Shinohara, and H.Furuya: "Conformation of 1,3-Dimethoxypropane in the Gas Phase and in Solution : Rotational Isomeric State Simulation of NMR Vicinal Coupling Constants" J.Mol.Struct.350. 129-134 (1995)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] A.Abe, H.Furuya, N.Ichimura, and S.Kawauch: "Gas Phase NMR and ab Initio Molecular Orbital Calculations of 5-Methoxy-1,3-dioxanes : A Critical Survey on the Gauche Effect" J.Mol.Struct. (in press).

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1996 Final Research Report Summary
  • [Publications] Y.Maeda: "High Pressure Differential Thermal Analysis of Dimer Liquid Crystals : α,ω-Bis[(4,4^1-cyanobiphenyl)oxy]alkanes" Liquid Crystals. 21. 365-371 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] A.Abe: "PVT Studies on Dimer Liquid Crystals and Estimation of Transition Entropies at Constant Volume,Macromolecules 28,pp90-95 (1995)(Correction)" Macromolecules. 29. 3337-3337 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] A.Abe: "Spatial Configuration of Chain Molecules Incorporated in Liquid Crystals and Thermodynamic Significance" Makromol.Symp.

    • Related Report
      1996 Annual Research Report
  • [Publications] A.Abe: "PVT Studies on Dimer Liquid Crystals Estimation of Transition Entropies at Constant Volume" Macromolecules. 28. 90-95 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A.Abe: "Calculation of the Conformation Entropy of Dimer Liquid Crystals and Comparison with the Observed Transition Entropies at Constant Volume" Macromolecules. 28. 96-103 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] H.Furuya: "Dipole Moment and Optical Anisotropy Studies of Mesogenic Twin Compounds, α, ω-Bis【(4, 4'-cyanobiphenyl)oxy】alkanes" J. Phys. Chem.99. 6483-6486 (1995)

    • Related Report
      1995 Annual Research Report
  • [Publications] A.Abe: "Thermodynamics and Molecular Ordering of Carbonate-type Dimer Liquid Crystals with Emphasis on the Geometrical Characteristics of the Linking Group" Acta Polymer.46. 437-444 (1995)

    • Related Report
      1995 Annual Research Report

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Published: 1995-04-01   Modified: 2016-04-21  

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