本研究利用活性自由基聚合法合成隨機排列式共聚物，再將隨機排列式共聚物polystyrene-random-poly(2-vinylpyridine) (PS-r-P2VP)與團聯式共聚物(PS-b-P2VP)摻合，藉由不同的摻合比例和分子量變化，研究摻合物的微相分離結構。
　　研究結果得知，使用小分子量隨機排列式共聚物可形成uniform solubilization，而本系統中，Mnb/Mnr必須控制在30以上(Mnb為團聯共聚物分子量，Mnr為隨機排列式共聚物分子量)，才能得到較明顯的結構變化，當 Mnb/Mnr～200，隨機排列式共聚物可以分散於PS-b-P2VP中，且使微相區域厚度變小。
　　當Mnb/Mnr～30，且隨機排列式共聚物其中之一成份比例為100%時，可形成有序有序轉換；對稱式隨機排列式共聚物(含有50% PS與P2VP之隨機排列共聚物)可以最有效的進入兩相界面區，摻合物結構維持層狀結構，厚度隨摻合比例提高而下降；添加一成分比例為75%之非對稱式隨機排列共聚物，同時有均聚物與對稱式隨機排列共聚物之行為，整體微相區厚度與摻合前相同；添加一成分比例為66%之非對稱式隨機排列共聚物，摻合少量時，其行為較類似對稱式隨機排列共聚物，微相區厚度變小，摻合大量時，其行為較類似一成分比例為75%之非對稱式隨機排列共聚物，微相區厚度最終趨於與摻合前相同。
　　當Mnb/Mnr～13與Mnb/Mnr～8時，對稱式隨機排列式仍可分佈於兩相界面區，但僅有少於10%可分散於兩相界面區，添加更多隨機排列共聚物僅形成巨觀相分離，這是由於兩相界面區因隨機排列共聚物鏈段太長無法溶入太多。
　　當Mnb/Mnr～3時，均聚物僅少部份分佈於微相區，大部份產生了巨觀相分離，對稱隨機排列式共聚物也僅少部份分佈於微相區，大部份形成巨觀相分離，而非對稱隨機排列共聚物則完全無法分佈於兩相界面區或微相區，僅形成巨觀相分離，且層狀厚度未改變。當分子量Mnb/Mnr＜3，對稱式隨機排列式共聚物僅有少量可以分散於兩相界面區，結構仍保持層狀結構，無法形成有序有序轉換或有序無序轉換。

Polystyrene-block-poly(2-vinylpyridine) (PS-r-P2VP) was synthesized by stable free-radical　polymerization (SFRP). As prepared PS-r-PVP was then blended with PS-b-P2VP to study the microphase separated structure with respect to the molecular weight and composition of PS-r-P2VP.
　　It was obtained that the uniform solubilization of PS-r-P2VP in PS-b-P2VP can be achieved when the molecular weight of random copolymers is very small. In our system, the morphological transition occur when Mnb/Mnr is smaller than 30 (Mnb is the molecular weight of block copolymer, Mnr is the molecular weight of random copolymer). As Mnb/Mnr～200, random copolymers distributed at the interface between PS and P2VP, and the domain size of blends became smaller.
　　When Mnb/Mnr～30, the addition of homopolymers induced an order-order transition. Symmetrical random copolymer (with the incorporation of random copolymers with 50% polystyrene) effectively distributed at the interface between PS and P2VP. The blends formed a lamellar structure and domain size decreased with increasing the content of PS-r-P2VP. Asymmetrical random copolymers with 75% PS or P2VP, its behavior between homopolymers and symmetrical random copolymers, so its domain size is invariant. As asymmetrical random copolymers with 66% PS, add 20% into block copolymer, it acts like symmetrical random copolymers, but add 30% into block copolymer, it acts like asymmetrical random copolymers with 75% PS or P2VP, and finally domain size is invariant.
　　When Mnb/Mnr～13 or Mnb/Mnr～8, less than 10% symmetrical random copolymers could distribute at the PS-b-P2VP interface. The addition of higher content of random copolymers cause macrophase separation, due to the large chain length of PS-r-P2VP.
　　When Mnb/Mnr～3, less than 10% homopolymer could distribute at the microphase. The addition of higher content of homopolymer cause macrophase separation. Less than 10% symmetrical random copolymers could distribute at the PS-b-P2VP interface. The addition of higher content of random copolymers cause macrophase separation. Asymmetrical random copolymers cause macrophase separation and domain size is invariant. When Mnb/Mnr＜3, only 10% symmetrical random copolymers could distribute at the PS-b-P2VP interface. The blends formed a lamellar structure rather than order-order transition or order-disorder transition.

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