本研究探討在poly(styrene-block-ethylene oxide) (PS-b-PEO)中分別加入sodium dodecyl sulfate (SDS)、poly(styrene-block-acrylic acid) (PS-b-PAA)及poly(styrene-graft-acylic acid) (PS-g-PAA)之雙成分混摻物的相行為與結晶行為。在PS-b-PEO/SDS的混摻系統中，由PEO鏈段與SDS所形成的complex會影響混摻物的有序無序相轉換溫度(TODT)。當SDS混摻比例提高時，complex結構消失之溫度會上升，導致TODT也隨之上升。在PS-b-PEO/PS-b-PAA的混摻系統中，PEO與PAA鏈段所形成的氫鍵會增加混摻物的相容性，使PS-b-PAA坐落於PS-b-PEO所形成微相結構的界面上，其中，PAA鏈段與PEO鏈段共享一個微域與PS鏈段微域形成微相分離。然而，當PS-b-PAA混摻比例提高時，PS-b-PAA的界面相容率達到飽和，使部分的PS-b-PAA無法坐落於PS與PEO鏈段的界面上，導致混摻物結構形成兩種不同層狀結構共存的巨觀相分離。在PS-b-PEO/PS-g-PAA混摻系統中，PS-g-PAA坐落在PS-b-PEO的界面上，然而PS-g-PAA的分子結構除了會造成界面曲率改變，也會使界面相容率更快達到飽和，導致部分的PS-g-PAA形成微胞坐落於PS的微域裡，而使混摻物隨著PS-b-PEO分子量的不同而出現不同的微結構，甚至產生巨觀相分離。此外，PS-b-PEO/PS-b-PAA及PS-b-PEO/PS-g-PAA混摻系統之巨觀相分離結構中的兩種結構比例會受到熱退火溫度的影響而改變。再者，PEO與PAA所形成的氫鍵會減少PEO可結晶的鏈段及阻礙PEO結晶，使混摻物的結晶溫度降低且結晶速率變慢。

We investigated the phase and crystallization behaviors of binary copolymer blends composed of poly(styrene-block-ethylene oxide) (PS-b-PEO) and the other component including sodium dodecyl sulfate (SDS), poly(styrene-block-acrylic acid) (PS-b-PAA), and poly(styrene-graft-acrylic acid) (PS-g-PAA). In PS-b-PEO/SDS complexes, the complexation between PEO chains and SDS affected the order to disorder transition temperature (TODT) of the complexes. In PS-b-PEO/PS-g-PAA blends, PS-g-PAA was located at the PS-b-PEO interface because of the hydrogen bonds between PEO and PAA chains. However, the incorporation of the branched molecular structure of PS-g-PAA into PS-b-PEO increased the interfacial curvature and decreased the saturation amount of PS-g-PAA at the PS-b-PEO interface. The residual PS-g-PAA formed micelles and segregated in to the PS microdomains, resulting in changes in morphologies, and the resulting morphologies depended on the molecular weight of PS-b-PEO. In PS-b-PEO/PS-b-PAA blends, the hydrogen-bonding interaction between PEO and PAA block chains improved the miscibility of the two copolymers. As a result, PS-b-PAA was located at the interface between PS-b-PEO microdomains, where PEO and PAA shared the common microdomain and they microphase-separated against the microdomain composed of PS blocks. However, when the concentration of PS-b-PAA was increased, some of PS-b-PAA could not be incorporated into the interface between PS and PEO microdomains. Such behavior caused macrophase separation, forming two types of lamellar structures with different domain sizes. Additionally, annealing temperatures affected macrophase-separated morphologies in PS-b-PEO/PS-b-PAA blends and PS-b-PEO/PS-g-PAA blends. Furthermore, hydrogen bonds decreased the crystallizable chain length of PEO and suppressed the PEO crystallization, causing decreases in the crystallization temperature and crystallinity of the blends.

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