高分子間氫鍵作用力的基礎研究與應用

Abstract

在高分子的相關學科中，高分子摻合物的性質研究一直是一個相當重要的領域。而在有關高分子摻合的研究中，特殊相互作用(氫鍵、離子-離子相互作用等)和相溶性問題一直是一個相當有趣的課題。透過引入特殊作用，使不相溶體系轉化為相溶體系，是這二十年來高分子摻合物研究最豐富的成果方向之一。而在高分子間氫鍵作用力的聚摻研究中，Painter-Coleman association model (PCAM)是最能描述其交互作用力及熱力學性質的理論。因此在本研究中，我們將選用不同高分子氫鍵的施予體(donor)及受體(acceptor)進行摻合研究，利用PCAM探討高分子間氫鍵作用力的熱力學性質，並使用霍立葉紅外線光譜儀及固態核磁共振偵測聚摻合物中氫鍵的交互作用及分子運動行為。而本論文共分為5個部份: (1) 利用微分掃瞄卡計及紅外線光譜判斷高分子氫鍵施予體的酚醛樹脂，聚乙烯酚及苯氧基樹脂與聚己內酯之間的氫鍵作用力大小，並利用PCAM模型預測。 (2) 選用poly(2-vinylpyridine)及poly(4-vinylpyridine)與酚醛樹脂聚摻，並利用微分微分掃瞄卡計及紅外線光譜及PCAM模型分析比較立體障礙對於高分子間氫鍵作用力的影響。 (3) 對於兩個原本不相溶的高分子，分別引入高分子氫鍵的施予體或受體於主鏈上，與另一高分子氫鍵受體或施予體聚摻，並利用PCAM模型的預測與實驗的結果作一比較。 (4) 選用三個不同官能基的高分子聚摻，利用PCAM模型預測其交互作用力及相行為。 (5) 高分子間氫鍵作用力的應用，著重於高分子玻璃轉移溫度的提升。我們將比較利用高分子聚摻及作成共聚物之間的玻璃轉移溫度的差別。

The miscibility and specific interaction in polymer blends have been a topic of intense interest in polymer science due to the their potential applications. The miscibility of an immiscible blend enhanced by introducing a functional to one component capabling of forming hydrogen bonding with another component is the one of the major achievements during these twenty years in polymer blend. This type of interaction has been widely described in terms of association model by Painter and Coleman due to exactly prediction in most systems. Therefore, in this study, we will choose different hydrogen bonded donor or acceptor polymers to blend with another polymer and study the interaction and molecular mobility behavior by using Fourier transform infrared spectroscopy and solid-state nuclear magnetic resonance spectroscopy. The experiment work in this dissertation was divided into five areas: (1) The hydrogen bonding strength of poly(ε-caprolactone) (PCL) blends with three different well-known hydrogen bonding donor polymers [i.e., Phenolic, poly(vinyl-phenol) and phenoxy] were investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy and prediction by PCAM. (2) The effect of steric hindrance on hydrogen bonding and miscibility behaviors between poly(2-vinylpyridine) (P2VP) or poly(4-vinylpyridine) (P4VP) with phenolic resin were investigated by differential scanning calorimetry and Fourier transform infrared spectroscopy and prediction by PCAM. (3) Studying of the immiscible polymer binary blend is capabling of hydrogen bonding donor or acceptor functional on the polymer chain to blend with another polymer and using the PCAM prediction to compare with experimental result. (4) We choose three different functional group of polymer to blend each other and using the PCAM to predict the phase behavior. (5) The application in hydrogen bonded polymer interaction, especially in glass transition temperature increase. We will compare the glass transition temperature behavior difference between polymer blends and their corresponding copolymers.