戴子安Dai, Chi-An臺灣大學:化學工程學研究所翁士鈞Weng, Shih-ChunShih-ChunWeng2010-06-302018-06-282010-06-302018-06-282009U0001-0607200911224500http://ntur.lib.ntu.edu.tw//handle/246246/187013本研究以硬桿-柔曲團聯共聚高分子(rod-coil block copolymer)(poly(phenylene vinylene)-b-poly(2-vinyl pyridine))(PPV-b-P2VP)與界面活性劑十二烷基苯磺酸(dodecylbenzesulfonic acid，DBSA)形成錯合物，藉由P2VP與DBSA自我聚集行為形成似梳狀(rod-comb)的分子組態，進而產生兩種不同尺寸的相分離結構，其中較大尺寸的結構乃是由於團聯式共聚合物PPV-b-P2VP之不互溶分子鏈段所形成而較小尺寸的奈米結構為共聚合物之柔曲鏈段P2VP與界面活性劑DBSA所形成之梳狀超分子結構，此兩種不同尺寸的結構共存於一系統中，因而形成了階級性結構(hierarchical structure)或稱此系統為結構內結構(structure-within -structure) 在本研究中，主要在探討PPV-b-P2VP之柔曲鏈段在不同體積分率下與不同比例DBSA錯合系統之型態的變化，其P2VP柔曲鏈段體積分率分別為0.52與0.27，即52-PPV/2VP(DBSA)x與27-PPV/2VP(DBSA)x 2組系統，以小角度X光散射(SAXS)、廣角度X光散射(WAXS)、穿透式電子顯微鏡(TEM)及偏光顯微鏡(POM)來對各錯合系統之型態進行討論並以變溫SAXS與WAXS解析各種熱誘導相轉化程序，如有序-有序相轉換(order-order transition，OOT)與有序-無序相轉換(order-disorder transition，ODT)等。 在27-PPV/2VP (DBSA)x系統中，隨著DBSA比例增加，x=0.5時，系統由原先單一尺度的層狀(lamellar)結構轉變為兩種不同尺寸的層結構共存於系統中即 lamellar-within-lamellar。於x=1.0時，系統依舊保持著lamellar-within-lamellar的階級性結構，其中大尺寸層狀結構中包含P2VP鏈段被拉伸至極限所產生的P2VP(DBSA)雙層排列以及系統為降低自由能而行成的單層P2VP(DBSA)排列之兩種大尺寸結構。 而在52-PPV/2VP(DBSA)x系統中，隨著DBSA的比例增加，當x=0.143、0.4、0.6階段，系統由原先的單一尺度層狀結構轉變為lamellar-within-lamellar階級性結構，但其大尺寸結構逐漸由一規則且大範圍排列之層狀結構逐漸轉變為小區域的broken lamellar，當錯合量為x=0.8時，系統進入一混亂的過渡區，此時並無明顯的結構型態，最後當錯合物比例來到x=1.0時，系統由原先的lamellar-within -lamellar型態，經由有序-有序相轉換，形成cylinder -within-lamellar階級性結構，即PPV所形成的柱狀排列，被嵌於在含有小尺度層狀結構P2VP(DBSA)梳狀鏈段所形成的基質(matrix)中。I studied the supramolecular rod-comb block copolymers formed by complexa- -tion of an amphiphilic surfactant , dodecylbenzenesulfonic acid (DBSA) , with the poly(2-vinylpyridine) (P2VP) blocks in a rod-coil block copolymer , poly(phenylene vinylene)-b-poly(2-vinyl pyridine)(PPV-b-P2VP). The rod-coil copolymer complexes exhibited structure-within-structure morphology. On the larger block copolymer lenth scale , the PPV blocks are microphase-separated from the P2VP(DBSA)x blocks and the smaller-scale lamellar mesophase organized by the P2VP(DBSA) comb blocks. This thesis is dedicated to resolving the hierarchical structures of the rod-comb PPV-b-P2VP(DBSA)x supramolecular system. Small angle X-ray scattering (SAXS), wide angle X-ray scattering (WAXS) , transmission electron microscopy (TEM) and polarized optical microscopy (POM) have been used for the structure characterization. In particular, temperature-dependent SAXS and WAXS have been utilized to probe the thermally-induced phase transition processes such as order-order transition (OOT) and order-disorder transition (ODT). The effects of copolymer composition with volume fraction,f , of P2VP blocks of 0.27 and 0.52) and the complex compositon have been systematically investigated. In f=27-PPV/2VP(DBSA)x systems. For x=0.5 and x=1.0, the rod-comb diblocks copolymer both exhibited a lamellar-within-lamellar morphology. But when x=1.0, the block copolymer exhibits a lamellar structure with two length scales . The larger one consists of fully-stretched P2VP chain in a P2VP(DBSA) bilayer and the other one consists of fully-stretched P2VP chain in a P2VP(DBSA) single layer which was assumed to be alleviating system’s free energy. n f=52-PPV/2VP(DBSA)x systems. For x=0.143,0.4 and 0.6, the system’s morphology changes from a lamellar structure with only one length scale to lamellar-within-lamellar hierarchical structures. For x=0.8, a phase transformation reaction occurs and the resulting morphology can not be reaily defined. For x=1.0, the rod-comb diblocks copolymer exhibtd a cylinder-within-lamellar morphology, where the PPV cylindrical domain of ca. 8.2nm in diameter embedded in the matrix consisting of the lamellar mesophase with the interlamellar distance of ca. 2.9nm organized by the P2VP(DBSA) comb block.摘要 Ibstract III錄 V目錄 VII目錄 XII一章 緒論 1-1前言 1二章 文獻回顧 2-1團聯共聚高分子(block copolymer) 2-2 二級作用力的分類 4-3 高分子/界面活性劑錯合物介相結構形成之條件 6-3-1 界面活性劑對高分子主鏈之鍵結數目(σ) 6-3-2 高分子與界面活性劑間的鍵結作用力 9-3-3 極性-非極之排斥力(polar-nonpolar repulsion) 9-4 高分子/界面活性劑錯合物之超分子形態 11-5 疏狀高分子錯合物之自組裝行為 14-5-1氫鍵鍵結疏狀共聚物自組裝行為 14-5-2十二苯磺酸(DBSA)疏狀共聚物自組裝行為 15三章 實驗方法 29.1 實驗藥品 29.2 儀器設備 31.3合成DEH-PPV實驗步驟 32-3-1合成2,5-Di(2’-ethylhexyloxy)toluene 32-3-2合成2,5-Di(2’-ethylhexyloxy)-4-methylbenzaldehyde 33-3-4合成 Poly(2,5-di(2’-ethylhexyloxy)-1,4-phenylenevinylene) 35-4 陰離子聚合 36-4-1溶劑的純化 36-4-2單體之純化 36-4-3 尾端具活性陰離子之P2VP合成 37-5 合成塊狀共聚高分子DEH-PPV-b-P2VP 38-5-1 純化DEH-PPV的製備 38-5-2尾端偶合反應 38-6 DEH-PPV-b-P2VP/十二烷基苯磺酸(DBSA)錯合物配置 40四章 結果與討論 42-1 團聯共聚高分子DEH-PPV-b-P2VP合成之GPC鑑定 42-2 DEH-PPV-b-P2VP-DBSAx錯合物WAXS型態分析 43-3DEH-PPV-b-P2VP-DBSAx錯合物SAXS結構分析 46-4 TEM 型態分析 53-5 DEH-PPV-b-P2VP(DBSA)x雙折射性質分析 55五章 結論 57考文獻 59錄 6113939712 bytesapplication/pdfen-US團聯式共聚高分子梳狀高分子錯合物階級性結構結構內結構十二烷基苯磺酸block copolymercomb-like polymer complexhierarchical structuresstructure-within-structuredodecylbenzenesulfonic acidthesishttp://ntur.lib.ntu.edu.tw/bitstream/246246/187013/1/ntu-98-R96524022-1.pdf