1991 年度実績報告書

高分子固体の高次組識と力学的および電気的物性・機能との相関

研究課題

研究課題/領域番号	03205088
研究機関	大阪大学
研究代表者	小林雅通大阪大学, 理学部, 教授 (40028147)
研究分担者	金子文俊大阪大学, 理学部, 助手 (70214468) 田代孝二大阪大学, 理学部, 講師 (60171691)
キーワード	超延伸・高弾性率繊維 / 結晶モリフォロジ- / 遷移双極子相互作用 / ポリオキシメチレン / 分子運動 / 結晶弾性率 / 強誘電性液晶 / 相転移
研究概要	高分子固体の力学物性に及ぼす高次組織および分子運動の影響を定量的に評価する研究の一環として,結晶モルフォロジ-に大きく依存する赤外バンドの波数及び形状変化に着目してこの現象の分子機構を解明すると共に結晶モルフォロジ-評価の新しい分光学的手法を開拓した。また高分子結晶における熱的揺動の性質とそれによって生ずる結晶弾性率の低下について考察した。既にポリオキシメチレン(POM)など一連の高分子についてモルフォロジ-が伸び切り鎖晶からラメラ晶に移る際に分子鎖軸方向に遷移モ-メントを持つ赤外平行バンドが高波数側に大きくシフトしその形状も変化することを示したが,赤外バンドの振動子強度の絶対値側定と理論的考察によってこの極めて特異的なスペクトル変化は高分子結晶の形状とサイズに大きく依存する遷移双極子相互作用によって引き起されることを明らかにした。また平行バンドのプロフィル解析によって結晶モルフォロジ-を定量的に評価できることを示した。POM繊維の結晶弾性率は分光学的手法で求めた理論弾性率に比べて小さく,特に室温以上では理論値の50%程度に減衰する。これは結晶領域における分子鎖の回転的揺動によるものと考え、ラマンバンド幅の温度依存性を2種の力学モデル(siteーhoppingとBibrationーtorsionモデル)に基いて解析し,分子運動に関する種々の力学パラメタ-を求めてPOMの力学的および熱力学的性質との関連性について考察した。電気的物性に関しては強誘電性液晶における高分子効果を解明する目的で,低分子液晶(M1)とそれを側鎖に有する高分子液晶(P1)について多形構造と相転移挙動を比較考察した。P1において側鎖のmesogenが構成する層状構造はスメクチック相においてもM1の場合に比べて高い規則性を保つことが明らかとなった。

研究成果

(20件)

すべてその他

すべて文献書誌 (20件)

[文献書誌] M. Kobayashi: "MorphologyーDependent Anomalous Ferquency Shifts of Infrared Absorption Bands of Polymer Crystals:Interpretation in Terms of Transition DipoleーDipole Coupling theory" J. Chem. Phys.96. 748-760 (1992)
[文献書誌] K. Tashiro: "Theoretical Evaluation of threeーDimensional Elastic Constants of Native and Regenerated Celluloses:Role of Hydrogen Bonds" Polymer. 32. 1516-1526 (1991)
[文献書誌] K. Tahiro: "Vibrational Spectroscopic Study on Ferroelectric Phase Transition of Vinylidene FluorideーTrifluoroethylene Copolymers:2. Temperature Dependences of the FarーInfrared Absorption Spectra and Ultrasonic Velocity" Polymer. 32. 1017-1026 (1991)
[文献書誌] K. Tashiro: "LatticeーDynamical Prediction of the Limiting Young's Modulus of Liquid Crystalline Arylate Polymers;Comparison with typical RigidーRod Polymers" Polymer. 32. 454-463 (1991)
[文献書誌] M. Kobayashi: "Infrared and Raman Spectra of Macrocyclic Poly(oxymethylene)" Macromolecules. 24. 4796-4800 (1991)
[文献書誌] K. Tashiro: "Theoretical Young's Moduli of Poly(pーphenylenebenzobisthiazole)and Poly(pーphenylenebenzobisoxazole)" Macromolecules. 24. 3706-3708 (1991)
[文献書誌] T. Nakaoki: "Conformational Order in Crystalline States and Gels of Syndiotactic,Isotactic and Atactic Polystyrenes studied by Vibrational Spectroscopy" J. Mol. Struct.242. 315-331 (1991)
[文献書誌] J. Hou: "Xーray Structure Analyses and Vibrational Spectral Measurements of the Model compounds of the LiquidーCrystalline Arylate Polymers. 2.Structural Isomorphism in a Series of Model Compounds" J. Phys. Chem.95. 9561-9568 (1991)
[文献書誌] H. Hase: "Raman Study of Ethanol and Ethanlic Solutions of LiCl at Low Temperature" J. Phys. Chem.95. 8541-8546 (1991)
[文献書誌] Y. Itoh: "Brillouin Scattering Studies on Polytypes of Stearic Acid B Form" J. Phys. Chem.95. 1794-1799 (1991)
[文献書誌] K. Tashiro: "Structure and Thermochromic SolidーState Phase Transition of Poly(3ーalkylthiophene)" J. Polym. Sci.,Part B Polym. phys.29. 1223-1233 (1991)
[文献書誌] K. Tashiro: "Structural Changes Occurring in the Phase transition of Ferroelectric Liquid Crystals[1]Temperature Dependence of the Xーray Diffraction and FtIR/Raman SPectra" Mol. Cryst. Liq. Cryst.200. 571-574 (1991)
[文献書誌] K. Tashiro: "Structural Changes in the thermochromic SolodーState Phase Transition on Poly(3ーalkylthiophene)" Synthetic Metals. 41ー43. 571-574 (1991)
[文献書誌] M. Kobayashi: "MorphologyーDependent Anomalous Frequency Shifts of IR Bands in Polar Polymer Crystals:Polytetrafluoroethylene" ReP. Progr. Polym. Phys. Jpn.34. 347-350 (1991)
[文献書誌] M. Kobayashi: "Molecular Motion in Trigonal Poly(oxymethylene)revealed by Vibrational Spectroscopy" Rep. Progr. Polym. Phys.Jpn.34. 351-354 (1991)
[文献書誌] T. Nakaoki: "Vibrational Spectra of Two Crystal Modifications of Syndiotactic Polystyreneーd_8" Rep. progr. Polym. Phys. Jpn.34. 355-358 (1991)
[文献書誌] T. Nakaoki: "Physical Gelation of Epimerized Polystyrenes" Rep. Progr. Polym.Phys. Jpn.34. 359-362 (1991)
[文献書誌] F. Kaneko: "Vibrational Spectroscopic Study on Crystal Growth of Stearic Acid B and E Forms" Rep. Progr. Polym. Phys. Jpn.34. 363-366 (1991)
[文献書誌] F. Kaneko: "Vibrational Spectroscopic Study on Mechanism of Solid State Phase Transitions of cisーUnsaturated Fatty Acids:Erucic Acid γ1→α1" Rep. Progr. Polym. Phys.Jpn.34. 367-370 (1991)
[文献書誌] K. Sato and M. Kobayashi: "Crystals 13" SpringerーVerlag, 41 (1991)

1991 年度 実績報告書

高分子固体の高次組識と力学的および電気的物性・機能との相関

研究代表者

小林 雅通 大阪大学, 理学部, 教授 (40028147)

研究成果

[文献書誌] M. Kobayashi: "MorphologyーDependent Anomalous Ferquency Shifts of Infrared Absorption Bands of Polymer Crystals:Interpretation in Terms of Transition DipoleーDipole Coupling theory" J. Chem. Phys.96. 748-760 (1992)

[文献書誌] K. Tashiro: "Theoretical Evaluation of threeーDimensional Elastic Constants of Native and Regenerated Celluloses:Role of Hydrogen Bonds" Polymer. 32. 1516-1526 (1991)

[文献書誌] K. Tahiro: "Vibrational Spectroscopic Study on Ferroelectric Phase Transition of Vinylidene FluorideーTrifluoroethylene Copolymers:2. Temperature Dependences of the FarーInfrared Absorption Spectra and Ultrasonic Velocity" Polymer. 32. 1017-1026 (1991)

[文献書誌] K. Tashiro: "LatticeーDynamical Prediction of the Limiting Young's Modulus of Liquid Crystalline Arylate Polymers;Comparison with typical RigidーRod Polymers" Polymer. 32. 454-463 (1991)

[文献書誌] M. Kobayashi: "Infrared and Raman Spectra of Macrocyclic Poly(oxymethylene)" Macromolecules. 24. 4796-4800 (1991)

[文献書誌] K. Tashiro: "Theoretical Young's Moduli of Poly(pーphenylenebenzobisthiazole)and Poly(pーphenylenebenzobisoxazole)" Macromolecules. 24. 3706-3708 (1991)

[文献書誌] T. Nakaoki: "Conformational Order in Crystalline States and Gels of Syndiotactic,Isotactic and Atactic Polystyrenes studied by Vibrational Spectroscopy" J. Mol. Struct.242. 315-331 (1991)

[文献書誌] J. Hou: "Xーray Structure Analyses and Vibrational Spectral Measurements of the Model compounds of the LiquidーCrystalline Arylate Polymers. 2.Structural Isomorphism in a Series of Model Compounds" J. Phys. Chem.95. 9561-9568 (1991)

[文献書誌] H. Hase: "Raman Study of Ethanol and Ethanlic Solutions of LiCl at Low Temperature" J. Phys. Chem.95. 8541-8546 (1991)

[文献書誌] Y. Itoh: "Brillouin Scattering Studies on Polytypes of Stearic Acid B Form" J. Phys. Chem.95. 1794-1799 (1991)

[文献書誌] K. Tashiro: "Structure and Thermochromic SolidーState Phase Transition of Poly(3ーalkylthiophene)" J. Polym. Sci.,Part B Polym. phys.29. 1223-1233 (1991)

[文献書誌] K. Tashiro: "Structural Changes Occurring in the Phase transition of Ferroelectric Liquid Crystals[1]Temperature Dependence of the Xーray Diffraction and FtIR/Raman SPectra" Mol. Cryst. Liq. Cryst.200. 571-574 (1991)

[文献書誌] K. Tashiro: "Structural Changes in the thermochromic SolodーState Phase Transition on Poly(3ーalkylthiophene)" Synthetic Metals. 41ー43. 571-574 (1991)

[文献書誌] M. Kobayashi: "MorphologyーDependent Anomalous Frequency Shifts of IR Bands in Polar Polymer Crystals:Polytetrafluoroethylene" ReP. Progr. Polym. Phys. Jpn.34. 347-350 (1991)

[文献書誌] M. Kobayashi: "Molecular Motion in Trigonal Poly(oxymethylene)revealed by Vibrational Spectroscopy" Rep. Progr. Polym. Phys.Jpn.34. 351-354 (1991)

[文献書誌] T. Nakaoki: "Vibrational Spectra of Two Crystal Modifications of Syndiotactic Polystyreneーd_8" Rep. progr. Polym. Phys. Jpn.34. 355-358 (1991)

[文献書誌] T. Nakaoki: "Physical Gelation of Epimerized Polystyrenes" Rep. Progr. Polym.Phys. Jpn.34. 359-362 (1991)

[文献書誌] F. Kaneko: "Vibrational Spectroscopic Study on Crystal Growth of Stearic Acid B and E Forms" Rep. Progr. Polym. Phys. Jpn.34. 363-366 (1991)

[文献書誌] F. Kaneko: "Vibrational Spectroscopic Study on Mechanism of Solid State Phase Transitions of cisーUnsaturated Fatty Acids:Erucic Acid γ1→α1" Rep. Progr. Polym. Phys.Jpn.34. 367-370 (1991)

[文献書誌] K. Sato and M. Kobayashi: "Crystals 13" SpringerーVerlag, 41 (1991)

1991 年度実績報告書

小林雅通大阪大学, 理学部, 教授 (40028147)