臺灣國際科展

含環胺-亞胺雙牙配基及其鎳錯合物的合成、結構鑑定,及烯烴催化聚合反應

科展類別
臺灣國際科展
屆次
2003年
科別
化學科
學校名稱
臺北市立第一女子高級中學
指導老師
陳竹亭、黃進松
作者
林倢予
關鍵字
環胺,亞胺,烯烴催化聚合
備註
加拿大二○○三年科學展覽會

摘要或動機

本研究合成含環形胺—亞胺雙牙配基鎳金屬催化劑,用以催化烯烴聚合反應。將2-甲基丙醛經由溴化、胺化及亞胺化的步驟合成含胺—亞胺的雙牙配基,Et2NCMe2CH=N(2,6-iPr2C6H3)
(3a)、(c-C4H8)N- CMe2CH=NPh (3b)、RNCMe2CH=N(2,6-Me2C6H3) (R = c-C4H8
3c,c-C5H10
3d)。再將配基和Ni(DME)Br2

(DME = 1,2- 二甲烷氧基乙烷) 反應, 形成鎳金屬錯合物Ni [Et2NCMe2CH=N(2,6-iPr2C6H3)]Br2 (4a)、Ni[RNCMe2CH=N
(2,6-Me2C6H3)]Br2 (R = c-C4H8
4c,c-C5H10
4d),並作結構鑑定。其中3b、3c、3d、4c、4d

均為合成的新化合物,4d
獲得X 光單晶繞射結構。


以合成之鎳錯合物作為催化劑,催化乙烯或降冰片烯(C7H10)的聚合反應,探討反應活性和高分子產物的性質。與含相同碳數的錯合物比較,在胺基具環形取代基的錯合物對乙烯的催化活性較佳,聚乙烯產物分子量較高,分子量分布範圍狹窄;其對降冰片烯的催化活性略遜於非環形者。同為環形取代基時,六環較五環者對乙烯的催化活性較差,但對降冰片烯的催化活性較佳。顯示乙烯聚合與降冰片烯聚合有不同的反應決定步驟。催化劑及配基的設計的確可以操控聚合反應及其高分子產物的性質。


The synthesis of α-amino aldeimines Et2NCMe2CH=N(2,6-iPr2C6H3)
(3a), (c-C4H8)NC
Me2CH=NPh (3b), RNCMe2CH=N(2,6-Me2C6H3)
(R = c-C4H8 3c,c-C5H10

3d), as well as the nickel complexes
Ni [Et2NCMe2C- H=N(2,6-iPr2C6H3)]Br2

(4a), Ni[RNCMe2CH=N (2,6-Me2C6H3)]Br2
(R = c-C4H8 4c,c-C5H10

4d) has been succeeded. Their structures were mainly determi ned by spectroscopy
or elemental analysis. The complex 4d was characterized by X-ray crysta llographic
analysis. It shows that the nickel complex has distorted tetrahedral configuration.


The catalytic reactions of ethylene or norbornene polymerization using the newly
synthesized nickel complexes are studied. All catalyts show high activity toward
studied olefin polymerization. Comparing the data of the catalytic ethylene polymerization
for complex 4c with those of its
isomer complex 4a, the former is
found to results in higher activity as well as the larger molecular weight of the
PE products with the narrower dispersity. On the contrary,
4c
shows lower activity in the reactions of norbornene polymerization
than 4a. For the cyclic amine derivatives,
4c of five-membered amino group
shows better catalytic activity toward ethylene polymerization than

4d
of six-membered amino group. But
4d
gives better perfomance for norbornene polymerization than
4c
. Such results indicate that the processes of ethylene and
norbornene polymerization might have different rate-determining steps. These study
confirms that the design of ligand and catalyst are crucial with respect to the
control of the catalytic olefin polymerization and the properties of the polymeric
products.



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