臺灣博碩士論文加值系統

本論文合成一新型之穩定劑12-phosphonic acid-dodecyl-2-bromo-2-methyl-propionic ester（PDBME），利用此穩定劑來穩定且改質氧化鐵顆粒，使氧化鐵顆粒成為可進行聚合反應之起始劑，由於PDBME結構具有油性鏈端，可使氧化鐵穩定分佈於CHCl3中，此分散劑同時也具有可以進行自由基聚合反應（ATRP）之官能基，PDBME可以由1H-NMR及31P-NMR來鑑定之。
我們可藉由活性自由基聚合反應（ATRP）於改質之氧化鐵表面聚合poly(t-butyl acrylate)（PtBA），於〔I〕：〔M〕＝1：2500比例下聚合反應成功地進行，並且可以經由控制反應時間，分別聚合出不同分子量，我們將氧化鐵以HCl處理之後，進行GPC量測得到PtBA之分子量（Mn）與分子量分佈（PDI）。之後進行水解反應將原本油溶性之PtBA水解得到水溶性的poly(acrylic acid)（PAA），可以由FT-IR來驗證其結果。
此製備方法可以確保每個核-殼顆粒僅包含一個磁性顆粒，而且外殼的高分子平均地包覆核心顆粒。最後，我們使用pyrrole單體在PAA鏈段上進行聚合反應得到PAA-PPy，使得磁性顆粒表面具有導電高分子，最後即得到核（磁性）-殼（導電性）型之core-shell nanoparticle，可經由NMR, dynamic light scattering, FT-IR, TEM, UV-vis和ESR來分析此材料。

The syntheses of stabilizer, 12-phosphonic acid-dodecyl-2-bromo-2-methyl-propionic ester (PDBME), have been developed. We modified the Fe3O4 nanoparticles by using PDBME and then made the particles able to be an initiator to process polymerizing. Because of the characteristic of PDBME, the Fe3O4 particles would disperse stable in CHCl3, and we utilized the functional group of PDBME to process ATRP, and 1H-NMR and 31P-NMR were used to demonstrate the PDBME.
The growing of poly(t-butyl acrylate) (PtBA) on Fe3O4 surface was processing successfully under the condition, 〔I〕：〔M〕＝1：2500, and we got sets of molecular weights (Mn) through controlling reaction time. Treating the core (Fe3O4) with HCl before GPC measuring and getting molecular weight and polydispersity (PDI) of PtBA. Hydrolysis was taken and water soluble poly(acrylic acid) (PAA) was got, the result was demonstrated by FT-IR.
This synthetic method ensures that each core-shell particle contains only one magnetic particle and that the polymer shell evenly encapsulates the core. Finally, we utilized pyrrole monomer to process in-situ polymerization on PAA chain to get conducting PAA-PPy. Consequently, core (magnetite)- shell (conducting PPy) nanoparticle was made up, and the thus-prepared materials were characterized by NMR, dynamic light scattering, FT-IR, TEM, UV-vis and ESR methods.

中文摘要............................................................................................. i
英文摘要............................................................................................. ii
誌謝.................................................................................................... iii
目錄... .iv
圖目錄 ...vi
表目錄 ...ix
第一章 緒論……………………………………………………….....1
1.1 前言……………………………………………………………....1
1.2 研究目的………………………………………………………....3
第二章 文獻回顧…………………………………………………….5
2.1 奈米材料…………………………..……………….…………..….5
2.2 磁性材料…….……………………………………………...…….15
2.3 氧化鐵………………………………………………….…..…......21
2.4 原子自由基聚合反應，ATRP.…………………………….…….23
2.5 導電性高分子…………………………………………………….32
第三章 實驗....................................................................................38
3.1 實驗藥品...................................................................................38
3.2 儀器...........................................................................................42
3.3 氧化鐵（Fe3O4）奈米顆粒製備...................................................44
3.4 合成12-phosphonic acid-dodecyl-2-Bromo-2-methyl-propionic ester，（PDBME）........................................................................45
3.5 製備Fe3O4/PDBME.......................................................................47
3.6 Fe3O4/PDBME/PtBA聚合反應.....................................................48
3.7 Fe3O4/PDBME/PAA水解反應......................................................48
3.8 Fe3O4/PDBME/PAA-PPy聚合反應...............................................49
第四章 結果與討論 …...50
4.1 10nm氧化鐵1（Fe3O4）顆粒之結構與性質分析……..……....50
4.2 12-hydroxy-dodecyl-2-Bromo-2-methyl-propionic ester，2之合成與分析…………………………………………………….……..54
4.3 12-phosphonic acid-dodecyl-2-Bromo-2-methyl-propionic ester，3 （PDBME）之合成與分析………………………………..…....56
4.4 Fe3O4/ PDBME之結構與性質分析………………………….......58
4.5 Fe3O4/PDBME/PtBA之結構與性質分析………………………..67
4.6 Fe3O4/PDBME/PAA之結構與性質分析………………………...77
4.7 Fe3O4/PDBME/PAA-PPy之結構與性質分析…………………...82
第五章 結論………………………………………………………....91
參考文獻……………………………………………………………....92

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