- 學位論文
利用Buchwald-Hartwig反應及Metallocene觸媒合成對位性立體規則性發光材料:立體規則性與鏈轉移反應效率控制
Preparation of Conjugated Amine Based Vinyl Monomers and Their Use in the Preparation of Stereoregular Fluorescent Polymers： Stereoregularity and Chain Transfer Efficiency Controls
摘要
有機光電材料的開發是過去二十年化學研究的重要項目之一。，用於有機發光二極體、太陽能電池及導電高分子材料之應用。共軛高分子可因共軛基團的共軛位置大概區分為主鏈共軛及支鏈共軛。而本研究將藉由實驗室多年來學長姐所建立的高分子合成技術以合成新型具備立體規則性支鏈共軛發光聚合物材料。因此，本研究將利用中鈀觸媒系統(Pd(OAc)2/(2-Biphenyl) di-tert-butylphosphine)誘導4-溴苯乙烯與Indole進行胺化反應，合成具共軛結構之乙烯芳胺單體，然後再利用Metallocene)觸媒進行對位選擇性聚合乙烯芳胺單體，使對位性聚乙烯芳胺不但具有發光性質並具備對位立體規則性。而研究的內容則包含下列三個方向： (Ⅰ) 利用鈀金屬觸媒，誘導帶有Halides側鏈基之單體(4Br-S) 進行胺化銜接反應(coupling reaction)，以合成苯乙烯對位位置具有胺類取代基之乙烯基芳香單體 1-(4-vinylphenyl) –indole。 (Ⅱ) 所合成之共軛性芳香胺單體可利用Metallocene(Cp*Ti(OMe)3/MAO觸媒系統進行立體規則選擇性之聚合反應，並在反應過程中加入鏈轉移劑(dimethylphenylvinylsilane)控制高分子分子量分佈，並生成末端具備特定官能基之對位聚乙烯芳胺(e.g.,syndiotactic poly-1-(4-vinylphenyl)-Indole。 (Ⅲ) 本研究中還利用AlEt3作為co-initiator將其sP4VPIn-OH末端轉換成sP4VPIn-OAlEt2之macroinitiator以進行環酯類單體 ε-caprolacton的開環聚合反應，進行第二段嵌段高分子的鏈成長反應以合成出sP4VPIn-b-PCL嵌段共聚高分子，並控制其嵌段高分子分子量與分子量分佈，藉由核磁共振儀(NMR)、小角度X光散射儀(Small Angle X-ray Scattering)的分析下，我們可以確定嵌段高分子在自我組裝行為所形成之奈米微結構並觀察其微觀相分離行為。
並列摘要
Development of organic photovoltaic materials is one of the important project in the past two decades of chemical research as photovoltaic Materials can be used in material applications solar cell materials and conducting polymers. In general, conjugated polymers can be divided into two categories, including main-chain and side chain conjugated polymers. This study aims to synthesized novel side-chain conjugated polymers, which have the unique structure of maintaining a syndiospecific stereoregularity in their corresponding poly-1-(4-vinylphenyl)-indole conjugated side-chain. Accordingly, the homopolymer and block copolymers of syndiotactic poly-1-(4-vinylphenyl)-indole can be prepared and their corresponding photoluminescence properties can be examined in the due course. Three synthetic steps were used for the successful syntheses of syndiotactic poly-1-(4-vinylphenyl)-indole: (Ⅰ) 1-(4-vinylphenyl) –indole (monomer) was prepared by coupling 4-bromostyrene with indole via the palladium-catalyst-mediated Buchwald-Hartwig reaction. (Ⅱ) End-functionalized syndiotactic poly-1- (4-vinylphenylindole) (OH-capped-sP4VPIn) was synthesized by conducting the syndiospecific polymerization of 1-(4-vinylphenyl) –indole in the presence of vinylsialne (chain transfer agent) using syndiospecific metallocene complexes as catalysts. (Ⅲ) sP4VPIn-b-PCL was prepared by conducting the controlled-living ring opening polymerization of ε-caprolacton using the OH-capped-sP4VPIn as the macroinitiator. The resulting stereoregular diblock copolymers were found to possess precise chemical architectures (define chemical structures with narrow ranges of molecular weight distribution) and can be self-organized into consistent nanostructures as evidenced by Small Angle X-ray Scattering and Transmission Electron Microscopy studies.
參考文獻
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