利用後過渡金屬觸媒/甲基氧化鋁系統 進行聚烯烴及官能化烯烴共聚物之研究

The study of prepare polyolefin and functional polyolefin via late-transition metal catalyst/MAO system

莊貴琴(kuei-chin chuang)

指導教授 ： 江彰吉

中原大學/理學院/化學研究所/碩士(2003年)

https://doi.org/10.6840/cycu200300028

摘要

Metallocene 觸媒的發展打破了Ziegler-Natta 觸媒獨占聚烯烴生產的方式，開創了均相觸媒在聚烯烴材料上之獨特技術。而助觸媒(MAO)之角色扮演的徹底研究，提供了聚烯烴聚合反應機制的完善解釋，因此尋找新的均相觸媒成為第二波的研究熱潮。於本論文將分五個部分討論，以自行合成的鎳衍生物觸媒分別聚合出乙烯、乙烯與11-氯基十一烯共聚物和苯乙烯、苯乙烯與4-氯甲基苯乙烯共聚物、以及苯乙烯/4-氯甲基苯乙烯共聚物-接枝聚甲基丙烯酸甲酯。
第一部份是合成觸媒，利用配位基和含有金屬的化合物在室溫下反應攪拌20小時，得到橙色粉末，經由1H、13C-NMR鑑定結構。第二部分以後都是利用第一部份所合成的觸媒和MAO來聚合乙烯、乙烯與11-氯基十一烯共聚物和苯乙烯、苯乙烯與4-氯甲基苯乙烯共聚物、以及將氯甲基作為起始劑利用氯化銅觸媒進行分子轉移自由基聚合反應，加入甲基丙烯酸甲酯與4-氯甲基苯乙烯共單體，可以得到接枝共聚物。最後將聚合物經由NMR、DSC、TGA、GPC技術來探討共聚物的結構、分子量、熔點與結晶度等等的物性，由分析結果得知以第一部份所合成的觸媒，能順利聚合出線性低密度的聚乙烯和亂排的聚苯乙烯與具有官能基的共聚物。

關鍵字

官能化聚烯烴 ； 後過渡金屬觸媒 ； 共聚物 ； 聚苯乙烯 ； 聚乙烯 ； 聚烯烴

並列摘要

The methallocene catalysts system was succeed to develop the new polyolefin material application and break the polyolefin that was producted by the Zieglar-Natta catalyst system with convention . The metallocene catalyst is homogenerous and single activity site in the cationic polymerization. In this study, it contains five parts , self-synthetic
nickel derivatives catalysts to carry the homo- and co-polymerization of ethylene with 11-chloro-undecene and styrene with 4-chloromethyl styrene and styrene-co-4-chloromethyl styrene-graft-mehyl methacrylate.
The first part , synthesis catalyst , Ligand and metal compound were stir under nitrogen at room temperature for 20 hours , obtain orange color powder . The catalyst have been characterized by 1H- and 13C-NMR . The second part , ethylene and styrene were copolymerized in the presence of a nickel derivative catalysts based on N2NiCl2 / MAO . The graft copolymer would be prepared by atomic transfer radical polymerization (ATRP) , such as poly(styrene-co-4-chloromethyl styrene-graft-mehyl methacrylate) . NMR , DSC , TGA , GPC were employed to study the structure and character of the polymerization products , such as the structure , melt point and crystallization will be discussed . In conclusion , synthesis linear low-density polyethylene , atactic polystyrene and functional copolymer .

並列關鍵字

Polyolefin ； Late Transition Metal Catalyst ； Functional Polyolefin ； polystyrene ； polyethylene

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