Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3607
標題: PAAc/PNIPAAm/mPEG接枝高分子與PAAc於低pH水溶液之交互作用與微胞結構探討
Introductions of PAAc/PNIPAAm/mPEG Graft Copolymers and PAAc Homopolymers in Low pH Aqueous Phase and Their Micellar Structure Characterisation
作者: 陳沂瑋
Chen, Yi-Wei
關鍵字: complexes
氫鍵
homoPAAc
PNIPAAm
摻混
微胞
出版社: 化學工程學系所
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摘要: 本研究設計一個帶有酸鹼與溫度應答性之雙性高分子,利用poly(acrylic acid) (polyAAc)為主鏈,poly(N-isiopropylamide) (PNIPAAm)和poly(ethylene glycol) (mPEG)為側鏈之接枝高分子,於特定條件下高分子可自組裝形成核殼(core-shell)之微胞結構,藉由導入不同分子量之homopolymer polyAAc,探討其交互作用與微胞結構的變化。 利用1H-NMR核磁共振儀確定接枝高分子之結構組成;以動態光散射粒徑儀(DLS)探討homoPAAc與接枝高分子之交互作用及內部性質分析;經由穩態螢光光譜儀(Spectrofluorophotometer)探測分子內部結構之變化;以及變溫1H-NMR核磁共振儀分析高分子鏈段間轉移及交互作用。由研究中發現較長鏈段之homoPAAc與接枝高分子形成架橋效應(bridging),導致溫度超過PNIPAAm之最低臨界溶液溫度(LCST)時PNIPAAm無法有效聚集形成核殼(core-shell)結構;摻混短鏈段之homoPAAc使高分子間互相聚集,但隨著溫度上升高分子因疏水作用力收縮導致高分子間的連結破裂(fragmentation)。當溫度超過PNIPAAm之LCST,高分子之PNIPAAm側鏈聚集形成疏水核心,核心外由摻混之homoPAAc與PNIPAAm形成的complexes所構成,mPEG鏈段向外部水相伸展,形成近似於微胞之結構。
In this study, temperature/pH-responsive graft copolymer which comprising acrylic acid (AAc) as polymeric backbones and poly(N-isopropylacrylamide) (PNIPAAm) and mPEG as grafts can self-assemble into core-shell micelle structure at an elevated temperature in aqueous solution. In addition, the structural reorganization of polymer aggregates in aqueous phase in the presences of PAAc homopolymers (homoPAAc) of varying average molecular weights (15,000, 8,000 and 1,200 g/mol), respectively, at pH 3.0 was studied in order to get a better insight into the effects of hydrogen bonding and hydrophobic association between the PNIPAAm grafts and homoPAAc on the aggregate structure. In the presence of homoPAAc with the molecular weight of 15,000 g/mol, the aggregates become much large in size and insensitive to the temperature change in the range of 10~60 ℃ in the aqueous phase of pH 3.0 due to the extensive hydrogen bonding of homoPAAc with PNIPAAm grafts and the consequent bridging effect. For the mixtures of the graft copolymers with homoPAAc of Mw 8,000 and 1,200 g/mol, respectively, the aggregates undergo fragmentation at the temperature below 32 ℃, the lower critical solution temperature of PNIPAAm homopolymers, by partial breakage of hydrogen bonds between PNIPAAm grafts and homoPAAc chains as a result of the thermal-induced coil-to-globule transition of PNIPAAm grafts. With the temperature being further increased above 32 ℃, the aggregate structure is transformed into more core/shell like micelle architecture with the free PNIPAAm grafts as hydrophobic inner cores, hydrogen bonded homo-PAAc/PNIPAAm complexes as interfacial layers and mPEG grafts as hydrophilic shells in contact with water.
URI: http://hdl.handle.net/11455/3607
其他識別: U0005-0410200716593800
文章連結: http://www.airitilibrary.com/Publication/alDetailedMesh1?DocID=U0005-0410200716593800
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