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  • 學位論文

樹枝狀高分子(Hyperbranch-graft- (NIPAAm-co-IAM) copolymers)在溫感及pH敏感領域之應用

Synthesis and characterization of Hyperbranch-graft-(NIPAAm-co-IAM) copolymers via ATRP and applied in temperature and pH sensoring detection.

指導教授 : 芮祥鵬
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摘要


本實驗為一新穎、實用性高之溫度/pH敏感型高分子在水溶液中的特性探討,相較於線性高分子,我們利用其黏度小、溶解度高之樹枝狀高分子,做為高分子內部核心,並使用溫敏型高分子和pH值敏感型高分子共聚合接枝在外形成外殼。最後探討此雙敏感型高分子,依照不同之聚合比例在水溶液中的化學性質及物理性質。 本研究利用Hyperbranched bis-MPA polyester-16-hydroxyl,generation 2 (Hyperbranch) 和α-bromoisobutyryl bromide形成Macroinitiator (Hyperbranch-Br),並使用原子轉移自由基聚合法(Atom Transfer Radical Polymerization, ATRP)合成不同聚合比例之 N-isopropylacrylamide (NIPAAm)和4-amino-2-methylene-4-oxobutanoic acid (IAM)共聚物。利用NMR及FTIR探討Hyperbranch 共聚物之分子結構,並由GPC觀察出活性自由基聚合可有效的控制PDI值小於1.4。當改變pH值2-12、濃度1-10 wt%,結果表明提升IAM單體之莫爾比例LCST有明顯上升趨勢,最高至LCST≒43℃。其中,本研究之Hyperbranch-g-(NIPAAm-co-IAM)-3-1( H-3)水溶液,相變化溫度接近人體溫度,可有效用至藥物釋放等生醫材料。

並列摘要


In this work, a novel temperature/pH-responsive hyperbranched copolymer was synthesized via the Atom Transfer Radical Polymerization(ATRP). A macroinitiator was prepared by modifying a hyperbranched bis-MPA polyester-16-hydroxyl, generation 2 (Hyperbranch) and used as the core structure while the thermo-sensitive N-isopropylacrylamide (NIPAAm) or/and pH-sensitive 4-amino-2-methylene-4- oxobutanoic acid (IAM) copolymers was used as the arms. The molecular structure of hyperbranched copolymer was characterized by 1H NMR and FTIR, respectively. According to the analysis results from GPC, the PDI of the product was controlled below 1.4 by the Living Free Radical Polymerization. When pH and concentration were changed from 2 to 12 and 1 to 10 wt%, we found that LCST values were increased by increasing IAM molar ratio. These results revealed that the LCST of aqueous solution of Hyperbranch-N-I-3-1 is close to human body temperature and thus is possible to be further applied in biomaterial.

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