臺灣博碩士論文加值系統

本研究探討由具有活性聚合特性的陰離子聚合法所製備PS-b-PDMS嵌段共聚物，針對共聚物表面性質進行討論。由GPC的檢測結果，所合成出的產物之數量平均分子量在30000～80000之間，分子量分佈在1.033～2.276之間；從動態機械分析儀（DMA）的圖譜中找出PS-b-PDMS嵌段共聚物之軟、硬鏈段的Tg分別出現在約–120℃與95℃，並與H-NMR核磁共振的分析證實含有兩種聚合物結構。在溶液表面性質方面，由於聚矽氧烷本身具有較低的表面能，因此，隨著聚矽氧烷的含量增加時表面張力值則隨之下降，再從表面張力與濃度曲線中找出臨界微胞濃度（cmc），並且利用粒徑分析儀測量其微胞的粒徑。從結果中可發現，隨著濃度的提高微胞粒徑大小隨之增加，但超過臨界微胞濃度後的粒徑，由於微胞聚集嚴重，導致無法測得微胞正確的水力半徑（Rh）；而單一微胞粒徑藉由估算後約為10nm與動態光散射所測量的水力半徑（Rh）的結果較為接近。

This work synthesized polystyrene-b-polydimethylsiloxane block copolymers by living anionic polymerization of styrene and hexamethylcyclotrisiloxane, and investigated the surface properties of the block copolymers solutions. The number average molecular weights of PS-b-PDMS were 3×104~8×104 g/mole determined by gel permeation chromatography (GPC) and their polydispersities were between 1.033 and 2.276. The DMA and H-NMR analysis of PS-b-PDMS block copolymers confirmed that the products consisted of two different blocks.
In solution surface properties aspect, because the polydimethylsiloxane itself has a lower surface energy, therefore increasing the content of the polydimethylsiloxane comes after the decrease of the surface tension value. The critical micelle concentration (cmc) were determined by surface tension measurement and the size of micelle was measured by a particle size analyzer. The conclusion is that enhancing the copolymer concentration raises the size of suspending component but after surpassing a critical micelle concentration the size increases rapidly because the micelle agglomeration is serious, it is unable to obtain correct micelle hydraulic radius (Rh). The micelle size at CMC was estimated as 10nm, that result is close to that from dynamic light scattering measurment (Rh).

中文摘要.................................................Ⅰ
英文摘要................................................ Ⅱ
目錄.....................................................Ⅲ
圖目錄...................................................Ⅵ
表目錄...................................................Ⅹ
第一章 緒論...............................................1
第二章 簡介...............................................3
2-1 嵌段共聚物......................................3
2-2 有機矽高分子的介紹.............................4
2-3 聚苯乙烯/聚矽氧烷二嵌段共聚物................6
2-4 陰離子聚合基礎理論.............................8
2-4-1 聚合反應原理...............................8
2-4-2 陰離子聚合的起始反應......................9
2-4-3 陰離子聚合的成長反應.....................11
2-4-4 陰離子聚合的終止反應.....................11
第三章 文獻回顧..........................................13
3-1 合成嵌段共聚物的相關文獻....................... 13
3-1-1 陰離子聚合法合成二嵌段共聚物...........13
3-1-2 三嵌段共聚物的合成.......................19
3-1-3 均聚物的合成與特殊嵌段的合成方法.......21
3-2 二嵌段共聚物的表面性質....................... 26
3-2-1 表面張力的測量........................... 26
3-2-2 界面活性劑與臨界微胞濃度值............. 31
3-2-3 二嵌段共聚物微胞相關文獻............... 37
3-2-4 粒徑分析/動態光散射相關文獻.............40
3-2-5 PS-b-PDMS二嵌段共聚物的微胞尺寸計算......43
3-3 有機矽共聚物應用在樹脂改性的相關文獻....... 47
第四章 實驗方法..........................................50
4-1 實驗藥品....................................... 50
4-2 實驗儀器....................................... 52
4-2-1 合成的設備................................ 52
4-2-2 樣品處理的設備........................... 52
4-2-3 性質檢測的設備........................... 53
4-3 合成步驟.................................. 58
4-3-1 預先處理.................................. 58
4-3-2 嵌段共聚物的合成......................... 60
4-3-3 溶解沈澱析出程序......................... 63
第五章 結果與討論........................................65
5-1 PS-b-PDMS二嵌段共聚物的合成.................65
5-1-1 PS-b-PDMS二嵌段共聚物的分子量結果.....68
5-1-2 PS-b-PDMS二嵌段共聚物的結構鑑定.......72
5-2 PS-b-PDMS二嵌段共聚物表面性質檢測結果.....82
5-2-1 表面張力值的測定結果.....................82
5-2-2 PDMS含量與分子量對於表面張力的影響...88
5-2-3 分子量與臨界微胞濃度(CMC)的影響....... 91
5-2-4 PS-b-PDMS二嵌段共聚物的微胞粒徑.......93
5-2-5 PS-b-PDMS二嵌段共聚物的微胞尺寸計算.. 98
第六章 結論與建議......................................108
參考文獻................................................110
附錄A ..................................................114
附錄B ..................................................127
附錄C ..................................................133

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