高分子氫鍵三相混摻之相行為及相溶性探討

Abstract

近二十年來，透過導入特殊作用力，使得不相溶的摻合體系轉而成為相溶體系，已成高分子摻合研究最豐富的成果方向之一。最能描述高分子氫鍵摻合系統的模型為Painter-Coleman Association Model，因此在此篇研究中，我們利用此模型去探討三相高分子氫鍵摻合系統。在此，我們選用不同類型的三相氫鍵摻合系統，去說明在三相摻合裡可能發生的不同類型相圖。 首先，利用微分掃瞄熱卡計(DSC)及傅立葉紅外線光譜(FT-IR)探討Phenolic Resin/Poly(ethylene oxide)/Poly(ε-caprolactone) 三相混摻系統之相行為及氫鍵作用力。發現雖然個別的三對二相混摻系統皆為完全互溶，但在此三相混摻系統裡，由於” ”及”ΔK”效應而使得相圖內部存在著封閉不相溶迴圈(closed immiscibility loop)。且計算出Phenolic resin和Poly(ethylene oxide)之間的分子間作用力平衡常數。 其次，藉由微分掃瞄熱卡計(DSC)、傅立葉紅外線光譜(FT-IR)及偏光顯微鏡(OM)，探討Phenolic/Phenoxy/PVPh之三相氫鍵摻合系統的相溶性和氫鍵作用力。根據DSC的熱分析，每一三相氫鍵摻合系統的比例組成皆為單一玻璃轉移溫度(glass transition temperature)，指出其均為互溶的。各個二相摻合系統裡的分子間平衡作用常數(KA)，皆大於各別高分子的自身作用平衡常數(K2、KB)。

The miscibility of an immiscible blend was enhanced by introducing one component which can form hydrogen bonded with another component. It is the one of the major achievements during last twenty years in polymer blend. This type of interaction has been widely described in terms of association model by Painter & Coleman due to exactly prediction in most systems. Here, we describe the different ternary blend phase diagrams by selected various kinds of polymer blends. First, the phase behavior and hydrogen bonding in ternary polymer blends of phenolic resin, poly(ethylene oxide) (PEO) and poly(ε-caprolactone) (PCL) were investigated by using differential scanning calorimetry (DSC) and Fourier transform infrared spectroscopy (FTIR). Although all three binary blends are respective miscible, there exists a closed immiscibility loop in the phase diagram due to the so called “ ” and “ΔK” effects in this hydrogen bonded ternary polymer system. The inter-association equilibrium constant between phenolic resin and PEO can be indirectly calculated. Second, the miscibility and hydrogen bonding behavior of ternary hydrogen bonded blend of phenolic/phenoxy/PVPh was investigated by using differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FT-IR) and optical microscopy (OM). According to the DSC analysis, every composition of the ternary blend shows single glass transition temperature (Tg), indicting that this ternary hydrogen bonded blend is totally miscible in the amorphous phase. The inter-association equilibrium constant (KA) of each individually binary blend is higher than any self-association equilibrium constant (K2 and KB) of component.