1990 Fiscal Year Annual Research Report
高分子固体の高次組織と力学的および電気的物性・機能との相関
| Project/Area Number |
02205086
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| Research Institution | Osaka University |
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Principal Investigator |
小林 雅通 大阪大学, 理学部, 教授 (40028147)
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| Co-Investigator(Kenkyū-buntansha) |
金子 文俊 大阪大学, 理学部, 助手 (70214468)
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| Keywords | 超延伸・高弾性率繊維 / ポリオキシメチレン / 強誘電性液晶 / 力学物性 / モルフォロジ- / 相転移 / 分子運動 |
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| Research Abstract |
ポリオキシメチレン(POM)の超延伸・高弾性率繊維の力学物性とモルフォロジ-の相関を解明する研究の一環として,POM繊維の結晶モルフォロジ-を評価する新しい分光学的手法を開拓した。特定の対称種に属する赤外バンドの波数がモルフォロジ-によって大きくシフトする現象に着目して,線型および大環状POMについて振動数とモルフォロジ-との定量的関係を調べた。POM結晶が典型的な折れたゝみ鎖結晶(FCC)から伸び切り鎖結晶(ECC)に移るにしたがって,分子鎖軸方向に遷移モ-メントをもつA_2対称種の赤外バンドが最高105cm^<ー1>も低波数シフトする。この現象は一連の極性高分子結晶に共通して観測され,遷移双極子相互作用によって生ずることを明らかにした。このような赤外バンドの特異的な変化は大環状POMについても見出された。この波数変化はPOM繊維におけるモルフォロジ-の違いを知るのに利用できる。たとえば,A_2(4)バンドの波数はFCCで1002cm^<ー1>に現れるが伸長率λと共に低波数シフトし,λ【similar or equal】5で903,λ>20で899cm^<ー1>にシフトし針状結晶(ECC)の極限値897cm^<ー1>に近ずく。さらに,分子運動が力学物性におよぼす効果に関し,CH伸縮領域のラマンスペクトルおよび回転型格子振動の遠赤外バンドの温度変化から,130K以上で分子鎮軸回りの回転ゆらぎを生じ,これによって結晶弾性率の低下が起ることを明らかにした。
強誘電性液晶の相転移の分子機構に関し,一連の芳香族系強誘電性液晶分子について結晶から等方液体に至る相転移過程をX線回折および赤外・ラマン分光で考察した。結晶は複雑な固相転移過程を経て強誘電液晶相(S^*_c)へ転移し,ついで常誘電液晶相(Ch)へ移る。その間,層状構造の段階的変化と共にメソゲンであるビフェニル基のねじれなど分子内構造の変化を生ずることを示した。
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[Publications] M.Kobayashi: "Molecular Conformation in Glasses and Gels of Syndiotactic and Isotactic Polystyrenes" Macromolecules. 23. 78-83 (1990)
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[Publications] K.Tashiro: "Thermal Contraction and Ferroelectric Phase Transition in Vynilidene FluorideーTrifluoroethylene Copolymers.2.An Effect of Tensile Stress Applied in the Direction Perpendicular to the Chain Axis" Macromolecules. 23. 2802-2806 (1990)
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[Publications] M.Kobayashi: "HighーResolution Carbonー13 Nuclear Magnetic Resonance of Trigonal Poly(oxymethylene)" Macromolecules. 23. 3052-3055 (1990)
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[Publications] T.Ishioka: "SmallーAngle Xーray Scattering Study for Structural Changes of the Ion Cluster in a Zinc Salt of an EthyleneーMethacrylic Acid Ionomer on Water Absorption" Macromolecules. 23. 3184-3186 (1990)
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[Publications] K.Tashiro: "Xーray Structure Analyses and Vibrational Spectral Measurements of the Model Compounds of the LiquidーCrystalline Arylate Polymers.Finding Out the Raman Bands Characteristic of the Twisted Biphenyl Structure in Association with the SolidーtoーLiquid Crystalline Phase Transition" J.Am.Chem.Soc.112. 8273-8279 (1990)
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[Publications] K.Tashiro: "Electorchemically Initiated Polymerization Reaction of 4ーVinylpyridine on Silver Electrode Surface:Direct Observation by the SurfaceーEnhanced Raman Scattering Technique" J.Phys.Chem.94. 3197-3204 (1990)
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[Publications] K.Sato: "Structures and Transformation in Polymorphism of Petroselinic Acid (cisーωー12ーOctadecenoic Acid)" J.Phys.Chem.94. 3180-3185 (1990)
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[Publications] T.Nakaoki: "Thermoreversible Gelation of Isotactic and Atactic Polystyrenes:Structure of CrossーLinks" Rept.Progr.Poly.Phys.Jpn.33. 91-94 (1990)
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[Publications] K.Tashiro: "MicroーRaman Measurements of Single Filaments of Kevlar and Poly(ethylene Terephthalate) Fibers subjected to Tensile Load" Rept.Progr.Polym.Phys.Jpn.33. 165-168 (1990)
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[Publications] K.Tashiro: "LatticeーDynamical Calculations of Stressーinduced Vibrational Frequency Shifts [I] Polyoxymethylene and Isotactic Polypropylene" Rept.Progr.Polym.Phys.Jpn.33. 169-172 (1990)
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[Publications] K.Tashiro: "LatticeーDynamical Calculation of Stressーinduced Vibrational Frequency Shifts [2] Orthorhombic Polyethylene Crystal" Rept.Progr.Polym.Phys.Jpn.33. 173-176 (1990)
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[Publications] K.Tashiro: "Structural Study on Phase Transition in Ferroelectric Liquid Crystal [II] The Structural Changes revealed by XーRay Diffraction Measurements" Rept.Progr.Polym.Phys.Jpn.33. 177-180 (1990)
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[Publications] K.Tashiro: "Quasiharmonic Treatment of Infrared and Raman Vibrational Frequency Shifts Induced by Tensile Deformation of Polymer Chains" J.Polym Sci.,Part B,Polym.Phys.28. 2527-2553 (1990)
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[Publications] M.Kobayashi: "Molecular Motion of nーAlkane Chains in Urea Inclusion Adducts studied by Analysis of Raman Band Profiles" J.Chem.Phys.93. 4659-4672 (1990)
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[Publications] M.Shimomura: "Vibrational Spectroscopic Study on Lowーmolecularーweight Polyoxymethylene Diacetates" Polymer. 31. 1406-1410 (1990)
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[Publications] M.Shimomura: "Vibrational Spectroscopic Study on Poly(ethylene oxide) Crystals" Polymer. 31. 1411-1414 (1990)
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[Publications] M.Shimomura: "Morphological Dependence of Vibrational Spectra of Polyoxymethylene and Poly(ethylene oxide) Crystals" J.Appl.Polym.Sci.,Appl.Polym.Symp.43. 241-256 (1990)
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[Publications] F.Kaneko: "Structure of Stearic Acid E Form" Acta Crystallogr.C46. 1490-1492 (1990)
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[Publications] K.Tashiro: "Phase Transition and Structural Change in the Model Compounds of LiquidーCrystalline Arylate Polymers;EtーOCOーφーOCOーφーφ‥COOーφーCOCーEt [I] Xーray Structure Analysis and Vibrational Spectra of the α and β Crystal Forms" Rept.Progr.Polym.Phys.Jpn.33. 181-184 (1990)
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[Publications] M.Kobayashi: "Molecular Motion of nーAlkane Chains in Urea Adducts:Frequency Modulation of Alkane Vibrations caused by Anharmonic Coupling with Librational Motion" Rept.Progr.Polym.Phys.Jpn.33. 185-188 (1990)
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[Publications] T.Nakaoki: "SoildーState HighーResolution Carbonー13 Nuclear Magnetic Resonance of Stereoregular Polystyrenes" Rept.Progr.Polym.Phys.Jpn.33. 521-524 (1990)
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[Publications] T.Nakaoki: "Conformational Order in Crystalline States and Gels of Isotactic,Syndiotactic,and Atactic Polystyrenes" J.Mol.Struct.242. 315-331 (1991)
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[Publications] 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.
