原子轉移自由基(ATRP)合成可以製備接枝鏈段均勻的接枝共聚物，且接枝共聚物有自組裝行為(Self-assembly)的特性。本研究利用原子轉移自由基合成製備聚偏二氟乙烯接枝聚甲基丙醯酸甲酯的接枝共聚物，且利用接枝共聚物的自組裝行為的特性，製備達到100nm以下的相分離層級的接枝共聚物與PMMA複合膜。 本研究第一個部分以原子轉移轉移自由基合成製備聚偏二氟乙烯接枝聚甲基丙醯酸甲酯的接枝共聚物。第二部分利用高分子摻合的方式，接枝共聚物摻合聚甲基丙醯酸甲酯(PMMA)製備複合薄膜，以溶劑移除PMMA相，製備多孔型PVDF高分子薄膜。 由實驗結果可以得知，利用FT-IR、NMR及ESCA鑑定接枝共聚物結構，發現接枝共聚物含有聚偏二氟乙烯與聚甲基丙醯酸甲酯的特性，表示接枝聚合反應是可行的。由SEM觀察得知，薄膜截面孔洞大小在100nm以下，表示以接枝共聚物的自組裝行為(self-assembly)，使得接枝共聚物與PMMA複合膜達到100nm以下的相分離層級。且在特定比例PVDF：PMMA＝60:40比例下，薄膜截面孔洞大約介於20至50nm之間，且呈現互穿型多孔結構。 This research work concentrates on the graft-copolymer of which uniformly grafted chains were prepared by atom transfer radical polymerization. The graft copolymer has self-assembly characteristics. And by virtue of self-assembly, the domain size of phase separation of the graft-copolymer and PMMA composite membrane fell in the nano-scale range. The chemical structures were investigated by FT-IR、NMR and ESCA . And their physical properties measured with the aid of DSC, TGA, XRD etc. reflected the features influenced by the mutual compatibility and/or miscibility between PVDF and PMMA. The morphology of the prepared composite membranes were investigated by SEM. The size of connected pores observed in membrane cross-section fell in the range of about 20～100 nm. The result of homogeneous, uniform morphology proves that the system is greatly modified by the presence of the graft copolymer which is characterized by its self assembly behavior.
