Grignard Metathesis Chain-Growth Polymerization and Characterization of Monodisperse Main-Chain Liquid Crystalline Poly(p-phenylene)

本實驗研究是利用格林納 (Grignard) 置換鏈成長聚合法合成出ㄧ系列的聚對位苯高分子 (Poly(p-phenylene) ，PPP) 。透過此法為鏈成長的縮合聚合反應機制，將可得到具均一分子量分布 (monodisperse) 及分子量可藉由改變單體和觸媒比例而使其能預期控制的聚對位苯高分子，進而可更精確的研究及了解其性質。 將一系列不同分子量的聚對位苯高分子進行合成鑑定及基本的性質測試，比較其光學性質、熱性質及微結構現象的趨勢或差異性。包含以膠體滲透層析儀 (Gel Permeation Chromatography, GPC) 測量其分子量與分子量分布情形，透過紫外光-可見光光譜儀 (UV - vis Spectrophotometer) 和螢光光譜儀 (Photoluminescence) 量測其光學性質，利用熱重分析儀 (Thermogravimetric Analyzer, TGA) 與示差掃描熱量計 (Differential Scanning Calorimeter, DSC) 進行熱性質量測。並藉由小角度X光散射 (Small angle X-ray scattering, SAXS) 及廣角度X光散射 (Wide angle X-ray scattering, WAXS) 來觀測聚對位苯高分子的微結構排列情形及晶體結構，並發現此一尚未有文獻確切發表過的新現象，即小分子量PPP有液晶的產生，而高分子量的PPP卻無液晶生成，最後再經由偏光顯微鏡 (Polarized Optical Microscope,POM) 來觀察證實此液晶現象。 總結上述儀器分析結果的數據資訊，獲得以格林納置換鏈成長聚合法所合成出的不同分子量之聚對位苯高分子其基本特性與其微結構方面的認識，致使我們對PPP整體的性質研究探討有其更一步的發展。In this thesis, a series of monodisperse Poly(p-phenylene) (PPP) were synthesized by Grignard Metathesis chain-growth polymerization. Via this chain-growth polycondensation mechanism reaction, we could yield PPP with narrow polydispersity and that the molecular weight of PPP is controlled by the feed ratio of the monomer to the Ni catalyst. The synthesized PPP were characterized by using various techniques includihg Gel Permeation Chromatography (GPC) to ensure molecular weight and PDI, UV-vis Spectrophotometer and Photoluminescence (PL) to analysis optical characterization, Thermogravimetric Analyzer (TGA) and Differential Scanning Calorimeter (DSC) to analysis thermal property. Furthermore, via Small angle X-ray scattering (SAXS) technique and Wide angle X-ray scattering (WAXS) technique to study the crystalline structure of PPP nanostructure, and then observed the new phenomenon, the low molecular weight PPP could transfer to liquid-crystal, but the high molecular weight PPP couldn’t. In the end, we used Polarized Optical Microscope (POM) techniques to prove it.摘要……………….………………………..………………………......………………..Ibstract…..……………………………………………………………..……..……..II錄………………………………………………………………………………...….III索引………………………………...………………………..…………………..…VI索引…………………………………………………………………..............…..VIII一章 緒論 ………………………………………….…......………….……....……1二章 文獻回顧…………………………………………………………………….2 2-1 導電高分子......................................................................................................2 2-1-1 導電高分子簡介...................................................................................2 2-1-2 導電性高分子種類...............................................................................3 2-1-3 導電性高分子的特性...........................................................................5 2-1-4 導電高分子的應用...............................................................................6 2-2 Poly(p-phenylene) 聚對位苯 (PPP)…………………………………………9 2-2-1 Oxidative cationic polymerization…………….………………………9 2-2-2 Precursor route……………………………………………………….10 2-2-3 Suzuki coupling reaction……………………………………………..11 2-3 Grignard(格林納)置換反應聚合法................................................................14 2-3-1 反應機制.............................................................................................14 2-3-2 延伸應用於合成 Poly(p-phenylene)……………………………….16 2-4 陰離子聚合....................................................................................................18 2-4-1 陰離子起始劑.....................................................................................18 2-4-2 陰離子聚合之單體與反應機制.........................................................19 2-4-3 特殊尾端官能基之陰離子聚合.........................................................21三章 實驗…………………………………………….……………………..…24 3-1 實驗藥品........................................................................................................24 3-2 儀器設備........................................................................................................26 3-3 實驗步驟........................................................................................................27 3-3-1 Phenylene單體的合成........................................................................27 3-3-1-1 p-Dihexyloxybenzene (3)的合成與純化...............................27 3-3-1-2 1,4-Dibromo-2,5-dihexyloxybenzene (2)的合成與純化.......28 3-3-2 Poly(p-phenylene) (PPP)的聚合......................................................29 3-3-2-1 Poly(p-phenylene)…………………………………………..29 3-3-2-2合成具雙鍵的PPP………………………………………..…30 3-3-3 陰離子聚合.........................................................................................32 3-3-3-1 無水溶劑的製備...................................................................32 3-3-3-2 聚合用單體之純化...............................................................32 3-3-3-3 陰離子聚合反應步驟...........................................................35 3-3-4 合成嵌段式共聚高分子 PPP-b-P2VP……………………………..39 3-3-4-1 反應前PPP的製備................................................................39 3-3-4-2 PPP-b-P2VP的合成...............................................................40四章 結果與討論……………………………………………………………..…41 4-1 Poly(p-phenylene)合成之鑑定……………………………………………...41 4-1-1 單體合成之鑑定………………………………………………….…..41 4-1-1-1 p-Dihexyloxybenzene (3)合成鑑定………………………….41 4-1-1-2 1,4-Dibromo-2,5-dihexyloxybenzene (2)合成鑑定………….41 4-1-2 PPP合成之鑑定………………………………………………………42 4-1-2-1 PPP合成鑑定……………..……………..………………….42 4-1-2-2 改變單體與觸媒比例之GPC結果......................................43 4-2 嵌段式共聚高分子 PPP-b-P2VP合成之鑑定.............................................45 4-3 光學性質分析................................................................................................46 4-3-1 UV-vis光譜分析.................................................................................46 4-3-2 PL光譜分析........................................................................................46 4-4 熱性質分析……………………………………………………………....…47 4-4-1 TGA………………………………………………………………….47 4-4-2 DSC…………………………………………………………………..47 4-5 SAXS圖譜分析..............................................................................................49 4-6 WAXS圖譜分析.............................................................................................51 4-7 Polarized Optical Microscope影像分析.........................................................57五章 結論………………………………….……………………………………..60考文獻……………………………………….……………………………………61錄………………………………………..……………………………...…………64索引2.1 導電高分子……………………………………………….………………….....32.2 常見的導電高分子結構………………………………………………………..52.3 Synthesize PPP by oxidative cationic polymerization method………………..102.4 Synthesize PPP by precursor route method……………………………………112.5 Mechanism of the Suzuki coupling……………………………………………122.6 Monomer 1 synthesis…………………………………………………………..122.7 Synthesize PPP by Suzuki coupling reacation method………………………..132.8 Proposed Mechanism for the Nickel-Initiated Cross-Coupling Polymerization142.9 Mechanism of Chain-Growth Polymerization…………………………………152.10 Synthesize PPP by Grignard metathesis polymerization method…………….162.11 常見的陰離子聚合反應單體............................................................................202.12 陰離子聚合反應機制示意圖............................................................................212.13 Example of protected functional groups of anionic polymerization…………222.14 Deprotection of anionic polymerization……………………………………...233.1 Synthesis of p-Dihexyloxybenzene………………………………………….273.2 Synthesis of 1,4-Dibromo-2,5-dihexyloxybenzene………………………….283.3 Synthesis of Poly(p-phenylene)……………………………………………..293.4 Synthesis of PPP with vinyl-group………………………………………….303.5 monomer purification apparatus………………………………………………333.6 vacuum transfer apparatus……………………………………………………..353.7 Interaction between THF and sec-BuLi……………………………………….363.8 Anionic polymerization apparatus…………………………………………….383.9 Synthesis of PPP-b-P2VP by anionic polymerization…………………….394.1 GPC result of PPP…………………………………………………………...424.2 Molecular weight vs. different ratio of monomer to Ni(dppe)Cl2……………...444.3 SAXS spectra of PPP……………………………………………………...504.4 WAXS spectra of PPP (常溫)……………………………………………..534.5 WAXS spectra of PPP – 4.2K (變溫)…………………………………...554.6 WAXS spectra of PPP – 10.2K (變溫)………………………………….564.7 POM images of PPP – 10.2K……………………………………………...584.8 POM images of PPP – 4.2K……………………………………………….59A.1 1H-NMR spectrum of p-Dihexyloxybenzene……………………………….64A.2 1H-NMR spectrum of 1,4-Dibromo-2,5-dihexyloxybenzene……………….65A.3 GPC result of all synthesized PPPs…………………………………………66A.4 GPC result (UV-vis 254nm)…………………………………………………..67A.5 GPC result (UV-vis 375nm)…………………………………………………..68A.6 UV – vis spectra of PPP…………………………………………………..69A.7 PL spectra of PPP…………………………………………………………70A.8 TGA data plots of PPP (first step)………………………...………………...71A.9 TGA data plots of PPP (second step)……………………………………….72A.10 DSC data plots of PPP (cooling)…………………………………………..73A.11 DSC data plots of PPP (second heating)…………………………………..74A.12 layer-like structure model……………………………………………………75A.13 PPP主鏈及其側鏈整體形狀示意圖..............................................................76A.14 Orthorhombic crystal 結構示意圖.................................................................77A.15 Hexagonal 結構示意圖..................................................................................78索引3.1 起始劑使用體積與聚合分子量的計量關係式................................................374.1 GPC results of different amounts of Ni(dppe)Cl2 in the feed…………………4