利用有機茂金屬觸媒系統合成官能化聚丙烯及其與黏土混煉之研究

Synthesis of functional polypropylene by metallocene catalyst system and applications in PP/Clay nanocomposites

王雅梅(Ya-Mei Wang)

指導教授 ： 江彰吉

中原大學/理學院/化學系/碩士(2006年)

https://doi.org/10.6840/cycu200600506

摘要

摘要
本研究主要利用metallocene觸媒系統合成側鏈具有一級胺官能基之聚丙烯共聚物，含有胺基之共聚物將有較佳的可染性與反應相容性。此外胺基可增加聚丙烯與黏土間的作用力，而更進一步利用混煉的技術製備聚丙烯/黏土奈米複合材料。
利用rac-Me2Si-[2-Me-4ph(Ind)2]ZrCl2/MAO觸媒系統共聚丙烯單體與N-allyl-N,N-bis(trimethylsilyl)amine，得到側鏈上含有胺基之聚丙烯共聚物，本實驗將探討利用加入不同單體比例、反應溫度時間與MAO含量控制胺基在共聚物上的含量。合成出的聚丙烯共聚物於側鏈上帶有親水性NH3+除了可與無基層材表面作鍵結外，亦可與黏土層間的陽離子(Li+,Na+)作離子置換反應。而在另一端疏水性高分子量的丙烯長碳鏈則裸露在黏土外層，接著進一步與不含官能基之聚丙烯進行混煉，藉由雙螺桿的剪切力，使黏土一層一層的剝離分散於聚丙烯基材中，形成剝離狀(exfoliation)之奈米聚丙烯高分子材料。
藉由1H-NMR與FTIR作結構鑑定，以元素分析儀檢測胺含量，微差掃描卡計(DSC)和熱重分析儀(TGA)測定熱性質，再利用X光粉末繞射分析儀(XRD)計算黏土層間距離，並以穿透是電子顯微鏡(TEM)觀看黏土分散情形。

關鍵字

奈米複合材料 ； 配位聚合法 ； 有機金屬茂觸媒 ； 聚丙烯

並列摘要

Abstract
In this study, we synthesis the polypropylene which has the functional side chain with primary amine group by using metallocene catalyst. Such amino-functional copolymers can offer better dyeability and compatibility. Additionally, the amine-functional groups can increase the interaction between the polypropylene and clay, to further prepare the polypropylene/clay nanocomposites by extrude.
The side-chain functionalized PP-g-NH2 was synthesized by propylene and N-allyl-N,N-bis(trimethylsilyl)aminein rac-Me2Si-[2- Me-4ph-(Ind)2]ZrCl2/MAO catalyst system. The content of amine-group in the copolymer can be controlled in different molar ratio of comonomer, reaction temperature and the amount of cocatalyst MAO. The side hydyophilic NH3+ functional group could anchored the polypropylene chain on the inorganic surfaces, besides the copolymer could ion-exchanges the cations(Li+,Na+) located between the clay interlayers.The PP-g-NH3+/clay hybride was subsequently further extruded with a unfunctionalized-PP. The clay was dispersing in polypropylene by using twin-screw extruder of shear reaction.
Side-chain functionalized PP-g-NH2 copolymer were characterized by nuclear magnetic resonance (NMR),infrared spectroscopy (FT-IR),differential scanning calorimering(DSC) and thermogravimetric analysis (TGA).The contents of amino group in the copolymer were determined using elemental analysis (EA).Additionally, using X-ray diffraction(XRD) and transmission electron microscopy (TEM) to demonstrated the dispersity of clay in the PP/clay nanocomposite

並列關鍵字

nanocmposites ； meatllocene catalyst system ； propylene

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