Please use this identifier to cite or link to this item: http://hdl.handle.net/11455/3572
標題: 溫度/酸鹼應答型外層交聯式奈米膠粒之製備及結構探討
Preparation of Thermo-/pH-Responsive shell-crosslinked Nanoparticles and their Structural Characterization
作者: 湯發奮
Tang, Fa Fen
關鍵字: micelles;微胞;nanogel;LCST;hydrophobic;hydrophilic;shell cross linked;core-shell;奈米膠粒;低臨界溶液溫度;疏水性;親水性;外層交聯;殼-核
出版社: 化學工程學系所
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摘要: 
本研究以自由基聚合法製備一雙性接枝高分子,是以poly(acrylic acid) (PAAc)及methacryloyl ethyl acrylate (MEA)之共聚合高分子為主鏈,poly (N-isopropylacryamide) (PNIPAAm) 和poly (ethylene glycol) (PEG) 作為高分子之側鏈。此接枝高分子於特定條件下(pH 5.0、I=0.01 M,溫度為60 ℃),可於水溶液中自主排列形成微胞結構,並加入ammonium pexodisulfate (APS)將微胞外層vinyl group交聯,形成一穩定且具有溫度/酸鹼應答型外層交聯式奈米膠粒。
本研究利用1H-NMR核磁共振儀確定接枝高分子之結構與組成;及以UV/Vis之穿透度分析可知接枝高分子的LCST不受主鏈PAAc解離的影響。再藉由穿透式電子顯微鏡(TEM)觀察其奈米膠粒形態;且以動態光散射儀(DLS)、螢光光譜儀、電子順磁共振光譜分析(EPR)、變溫1H-NMR核磁共振儀等分析奈米膠粒於不同溫度與pH 值下其性質及結構變化。經由TEM影像觀察證實奈米膠粒為球形之core-shell結構;利用粒徑分析可證實奈米膠粒具有溫度及酸鹼應答特性。但由研究中發現奈米膠粒於不同pH值環境時,因水膠層之PAAc解離程度不同,造成核心變而大使內部PNIPAAm鏈段以不同方式聚集,於pH 3.0環境下核心大小不變且PNIPAAm鏈段是可與對面鏈段碰觸到,故以分子間聚集方式使粒徑收縮;於pH 5.0環境下核心部份會些微變大使PNIPAAm鏈段與對面鏈段無法碰觸到,而先與鄰近鏈段聚集使核心部份收縮,進而能與對面鏈段形成分子間聚集使粒徑收縮;於pH 7.0環境下核心部份變的更大使PNIPAAm鏈段無法與對面鏈段碰觸,而產生分子內聚集使無法造成粒徑收縮,且此時構形為近似中空之core-shell結構。

Thermo/pH-responsive nanogels were synthesized by radical polymerization of the methacryloyl ethyl acrylate (MEA) moieties of the graft copolymer comprising acrylic acid (AAc) and MEA units as the backbone and poly(N-isopropylacrylamide) (PNIPAAm) and mPEG as the grafts in micelle form in aqueous phase at high temperature. The nanogels with core-shell structure exhibit highly increased stability in comparison with their micelle precursors and temperature-dependent swelling behavior at pH below 5.0. The swelling also significantly changes in response to pH alteration, the extent being dependent on the cross-linking density of the nanogels. The raising ratio of solid/liquid-like core structure in the nanogels with increasing temperature is attributed to the continual dehydration of the PNIPAAm grafts. In addition, the increase in the degree of AAc residue dissociation with increasing pH raises the liquid-like core fractions due to the swelling of hydrogel layer and disruption of interchain hydrogen bonding. At pH 7, the more hydrated core inside the nanogels with surrounding dissociated PAAc hydrogel layer significantly reduces the interchain hydrophobic interaction of PNIPAAm grafts with increasing temperature, inducing the formation of hollow-like structure at high temperature.
URI: http://hdl.handle.net/11455/3572
其他識別: U0005-1707200617001100
Appears in Collections:化學工程學系所

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