高分子與過氯酸鋅間之離子作用力探討

Abstract

透過分子間的特殊作用力，能使得物質的物理性質產生改變，進而獲得新式的材料。藉由這種方式，將高分子加以混摻，可讓原本使用受限的材料，能應用在更廣泛的領域。本研究便是討論高分子與過氯酸鹽混摻後，彼此之間會形成離子作用力，並觀察所產生的作用力以及各種性質上的改變。 在poly(vinylpyridine)/zinc salt系統中，使用具有相同重覆單元(repeat unit)，但不同幾何結構的poly(4-vinylpyridine) (P4VP)與poly(2-vinylpyridine) (P2VP)。從微分掃瞄熱卡計 (Differential Scanning Calorimeter, DSC) 所得出的熱性質變化可以看出，在不同的結構影響下，產生的離子作用力會有所差別。而隨著鋅鹽的添加量上升，在傅立葉轉換紅外線光譜儀 (Fourier Transform Infrared Spectrophotometers, FT-IR)上可以明顯觀察到離子作用力的增強。電子能譜儀 (Electron Spectroscopy for Chemical Analysis, ESCA)則能進一步證明作用力的存在。除此之外，也利用交流電阻抗量測儀(Alternative Circuit Impedance, a.c. Impedance)觀察離子的導電度變化情形。另外，透過廣角度X-ray散射分析儀 (Wide Angle X-ray Diffraction, WAXD)來分析其中過氯酸鹽，在加入到高分子後，其結晶大多都已被破壞。最後由固態核磁共振 (Solid-state NMR)提供微相形態的證據。 其次，亦使用poly(N-vinyl-2-pyrrolidone) (PNVP)來進行傅立葉轉換紅外線光譜儀(FT-IR)及微分掃瞄熱卡計(DSC)的實驗，並從紅外線光譜比較各種不同氫鍵作用力與離子作用力之間吸收峰漂移大小的不同。

Various properties of polymer materials can be modified to fabricate a novel material through the specific molecular interactions. Blending of existence polymers is able to make widerly applications by this way. Both various physical properties and ionic interactions between polymers and zinc perchlorate were studied in this thesis. In the first place, the thermal properties, ionic interaction and morphology of the poly(vinylpyridine)/zinc salt blend system were investigated by differential scanning calorimeter (DSC), Fourier transform infrared spectrophotometers (FT-IR), Electron spectroscopy for chemical analysis (ESCA), a.c. impedance, Wide angle X-ray diffraction (WAXD) and Solid-state NMR. In addition, two polymers with the same repeat unit but different geometric structure, the so called poly(4-vinylpyridine) (P4VP) and poly(2-vinylpyridine) (P2VP), were studied the steric hindrance effect in ionic interaction between poly(vinylpyridine)/zinc salt blend system. The thermal properties observed through DSC indicate that the ionic interaction was influenced under different geometric structures. The ionic interaction in the FT-IR spectrum was increased with the increasing of the mole ratio of zinc salt. In addition, the ESCA also can further confirm the existence of ionic interaction between polymer and zinc salt. Besides, the ionic conductivity was observed by a.c. impedance. Furthermore, the microstructure and morphology in blending of polymer and zinc salt can be observed by WAXD and Solid-state NMR. The WAXD result shows that the crystalline phase of zinc salt was destroyed by blending with poly(vinylpyridine), indicating that the good miscibility in this polymer-salt mixture system. However, two-proton spin-lattice relaxation time in the rotating frame (T1ρ(H)) was observed in Solid-state NMR at higher zinc salt content, indicating that two micro phase separation above 2-3 nm occurs. Second, the DSC and FT-IR were performed to obtain the characteristic properties in the poly(N-vinyl-2-pyrrolidone)/zinc salt system. Furthermore, the magnitudes of various hydrogen bonding interactions and ionic interactions were compared by using the FT-IR analysis.