本研究探討不同分子量之團聯共聚物poly(styrene-block-ethylene oxide) (PS-b-PEO)與對稱型及非對稱型poly(styrene-block-acrylic acid) (PS-b-PAA)混摻之相行為與非等溫結晶動力學。以中、低分子量之PS-b-PEO混摻PS-b-PAA，結果顯示大部分的PEO與PAA鏈段形成分子間氫鍵，具有良好之相容性。但在大分子量之PS-b-PEO/PS-b-PAA混摻系統中，無論混摻對稱型或非對稱型PS-b-PAA，皆受到退火溫度及巨觀相分離的影響，使其氫鍵比例下降較多。
　　不同分子量之PS-b-PEO與PS-b-PAA混摻會產生不同型態的微相結構。小分子量之PS-b-PEO混摻對稱型PS-b-PAA，PEO與PAA之間之氫鍵作用力使PS-b-PEO之微相結構由無序轉變成有序；中分子量之PS-b-PEO混摻系統則是維持層狀結構；而大分子量之PS-b-PEO混摻對稱型PS-b-PAA後，則是因為兩高分子分子量之差異，故在20% PS-b-PAA添加量時混摻物出現巨觀相分離。在非對稱型混摻系統中，低分子量之PS-b-PEO在摻入PS-b-PAA後，隨著PS-b-PAA添加量的增加，其結構由無序轉變為球狀再轉變為層狀。中分子量之PS-b-PEO則是由於添加具長鏈段PS之PS-b-PAA，使PS微相的體積上升較多，故結構由層狀轉為柱狀。而大分子量之PS-b-PEO混摻非對稱型PS-b-PAA後，同樣由於兩高分子分子量差異大，因此相容性較差，故當PS-b-PAA占整體混摻系統40%時出現巨觀相分離。
　　由混摻物結晶行為可發現，不同分子量之PS-b-PEO混摻PS-b-PAA後，會因PAA之Tg效應及PEO與PAA之間的氫鍵作用力，造成PEO的結晶溫度、結晶度及結晶速率隨著PS-b-PAA添加量增加而下降。此外，大分子量之混摻系統與中、低分子量之混摻系統相比，其PEO結晶受到氫鍵作用力與PAA之Tg效應之影響較小。

We investigated the phase and crystallization behaviors of blends composed of poly(styrene-block-ethylene oxide) (PS-b-PEO) and poly(styrene-block-acrylic acid) (PS-b-PAA). When low-molecular-weight and medium-molecular-weight PS-b-PEO was blended with PS-b-PAA, most PEO chains formed hydrogen bonds with PAA chains, leading to the favorable compatibility of the copolymers. By contrast, the fraction of the hydrogen bonded PEO/PAA in the blends composed of high-molecular-weight PS-b-PEO was low, which was caused by the poor compatibility of the two copolymers and high annealing temperature.
The morphology of PS-b-PEO/PS-b-PAA blends strongly depended on the molecular weight of PS-b-PEO. When low-molecular-weight PS-b-PEO was mixed with symmetric PS-b-PAA, morphology of the blends changed from disorder to hexagonally packed cylinders because of the hydrogen-bonding interactions. In the blends containing medium-molecular-weight PS-b-PEO and symmetric PS-b-PAA, the morphology of the blends retained lamellae. By contrast, the high-molecular-weight PS-b-PEO/symmetric PS-b-PAA blends exhibited macrophase separation, which was induced by the high segregation strength of the blends. On the other hand, when low-molecular-weight PS-b-PEO was blended with asymmetric PS-b-PAA, the morphology of the blends changed from disorder to spheres, and to lamellae with an increase in the PS-b-PAA content. In the blends comprising medium-molecular-weight PS-b-PEO and asymmetric PS-b-PAA with long PS chains, the volume change in the PS microdomains with the addition of PS-b-PAA was more than that in the PEO/PAA microdomains, which resulted in the morphological transition from lamellae to cylinders. Similar to the high-molecular-weight PS-b-PEO/symmetric PS-b-PAA blends, the segregation strength of the high-molecular-weight PS-b-PEO/asymmetric PS-b-PAA blends was high, thereby causing macrophase separation of the two copolymers when 40 wt% PS-b-PAA was added.
Regarding the crystallization behavior of the PS-b-PEO/PS-b-PAA blends, the crystallization temperature, overall crystallization rate, and degree of crystallinity of PEO decreased with the addition of PS-b-PAA, which was attributed to the hydrogen-bonding interactions and high glass transition temperature (Tg) of PAA that hindered PEO crystallization.

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