邱文英2006-07-252018-06-282006-07-252018-06-282003-06http://ntur.lib.ntu.edu.tw//handle/246246/9349This study includes two parts, the first part is concerned with using 4-oxo-TEMPO to synthesize poly(butyl acrylate) (PBA) via nonisothermal process. At first, AIBN, 4-oxo-TEMPO, butyl acrylate, DDBSA and DMF were used to react under a two stage temperature, that is the reactants are hold at a temperature for hours then the temperature is raised to higher temperature, 147 ℃. In order to control the molecular weight and its distribution, the effect of the concentration ratio of 4-oxo-TEMPO to AIBN, solvent amount effect, preheating time, preheating temperature and content of DDBSA on the molecular weight characteristics of PBA were investigated. In the second part, PS and PBA macroinitiators are used to synthesized PS-b-PBA and PBA-b-PS diblock copolymer, respectively. In experiment analysis, conversions were measured by TGA, molecular weight and its distribution were measured by GPC, and the relation between molecular weight and conversion was used to ascertain if the polymerization is undergone in a living manner. NMR was used to identify the structure of PBA after the preheating step. NMR and UV are used to discuss the concentration change of initiator and stable free radical concentrations, respectively.本研究包含兩部分，第一部分利用活性自由基合成方法， 經由非恆溫過程合成聚丙烯酸丁酯(PBA)。首先以AIBN ， 4-oxo-TEMPO ，丙烯酸丁酯(BA)，以及少量DDBSA 與溶劑DMF 在兩階段的反應溫度下進行反應來合成活性PBA ，反應溫度先 在某一預熱溫度下預熱再提升到最終反應溫度147 ℃。 為了控制分子量的大小與分佈，本研究改變起始劑AIBN 濃度、4-oxo-TEMPO/AIBN 比值、溶劑含量、預熱時間及加入 有機酸DDBSA 的含量，以探討其對分子量大小及分佈特性之 影響。第二部分則分別使用PS 及PBA 巨起始劑合成PS-b-PBA以及PBA-b-PS 雙區塊共聚物。實驗分析利用TGA 測量活聚物的轉化率，利用GPC 測量 其分子量大小及分布，藉由分子量大小與轉化率是否呈線性關 係來判斷是否合成活聚物，再利用NMR 鑑定預熱過後PBA 之 結構，NMR 及UV 則分別用於研究起始劑及穩定自由基的濃度 變化。實驗中並發現在第二段反應溫度再添加有機酸可以有效 地促進分子量的成長，此外，穩定自由基與起始劑(或巨起始劑) 的比值要大於或等於1.3(1.2)方能有效的控制聚合反應。application/pdf2696780 bytesapplication/pdfzh-TW國立臺灣大學化學工程學系暨研究所reporthttp://ntur.lib.ntu.edu.tw/bitstream/246246/9349/1/912216E002016.pdf