含同位聚1-丁烯之具立體規則性雙嵌段共聚高分子:合成方法與奈米結構自組裝研究

Stereoregular Diblock Copolymers of Isotactic Poly(1-butene) : Syntheses and Self-Assembly Nanostructures Studies

薛俊廷(CHUN-TING HSUEH)

指導教授 ： 蔡敬誠

國立中正大學/工學院/化學工程學系/碩士(2016年)

摘要

本研究中使用金屬茂觸媒系統([Bis(indenyl)dimethylsilane]ZrCl2,
[Bis(2-Methyl-4-phenylindenyl)dimethylsilane]ZrCl2及Dichloro[rac-ethylenebis(indenyl)]zirconium(IV))進行同位性聚1-丁烯(Isotatic poly(1-Butene)，iP1B)的合成，藉由導入鏈轉移劑(三乙基鋁)以末端官能化同位聚1-丁烯(形成鋁官能基末端)，並且經由氧氣及雙氧水的氧化反應可有效得到末端具有氫氧基的同位性聚1-丁烯(hydroxyl-capped iP1B，iP1B-t-OH)。我們藉由改變其鏈轉移劑用量及反應溫度，可以探討其分子量變化及β-H消去反應的現象。
本研究中還加入Tin(異鋅酸亞錫)觸媒將iP1B-t-OH轉換成macroinitiator進行環酯類單體L-lactide的開環聚合反應，以合成出iP1B-b-PLLA之嵌段共聚高分子。藉由凝膠滲透層析儀(GPC)、核磁共振儀(NMR)、小角度X光散射儀(Small Angle X-ray Scattering)及穿透式電子顯微鏡(TEM)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。

關鍵字

嵌段共聚高分子 ； 立體規則性高分子 ； 鏈轉移劑 ； 小角度X光散射儀

並列摘要

In this study, we report that by conducting the isospecific Poly(1-Butene) polymerization in the presence of chain transfer agent (triethylaluminum) using rac-Me2Si(Ind)2ZrCl2,rac-C2H4(Ind)2ZrCl2 and rac-Me2Si(2-methyl-4-phenylInd)2ZrCl2 as the isospecific metallocene catalyst can result in the generation of aluminum-capped isotactic poly(1-Butene) as the exclusive chain transfer reaction product. The resulting aluminum-capped iP1B can be treated with oxygen and hydrogen peroxide to provide the hydroxy-capped iP1B (iP1B-t-OH) as the end-functionalized prepolymer.
We also demonstrate that the hydroxyl end-group of the iP1B-t-OH can be used to undergo living ring opening polymerization of L-lactide; thus, novel stereoregular diblock copolymers, iP1B-block-PLLA, can be successfully prepared with high yield. Our studies clearly demonstrated that using the iP1B-t-OH as the macroinitiator for conducting the subsequent postpolymerization reactions can led to the successful preparations of novel stereoregular diblock copolymers.

The resulting stereoregular diblock copolymers 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.

並列關鍵字

Diblock Copolymer ； Small Angle X-ray Scattering ； Stereoregular Polymer ； Chain Transfer Agent

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