Tridentate [N,N,O] Schiff-base group 4 metal complexes: Synthesis, structural characterization and reactivity in olefin polymerization

被引:35
|
作者
Paolucci, Gino
Zanella, Alessandra
Sperni, Laura
Bertolasi, Valerio
Mazzeo, Mina
Pellecchia, Claudio
机构
[1] Univ Ca Foscari, Dipartimento Chim, I-30123 Venice, Italy
[2] Univ Ferrara, Dipartimento Chim, I-44100 Ferrara, Italy
[3] Univ Ferrara, Ctr Strutturist Diffrattometr, I-44100 Ferrara, Italy
[4] Univ Salerno, Dipartimento Chim, I-84081 Baronissi, SA, Italy
关键词
titanium; zirconium; hafnium; polyethylene; polypropylene; phenoxyimine catalysts;
D O I
10.1016/j.molcata.2006.05.043
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
New complexes LTiCl3(1), LZrCl3(2) and LHfCl3(3) (L = (E)-2-tert-butyl-6 [(quinoline-8-yl imino)methyllphenol ate) have been synthesized and fully characterized by multinuclear NMR, mass spectrometry and X-ray diffractometry. The three isostructural complexes show distorted octahedral geometries. Complexes 1-3 were tested as catalysts for ethylene polymerization under a variety of experimental conditions. Reasonable productivities were achieved after activation by methylaluminoxane (MAO) under moderate temperature and pressure conditions (e.g., 50 degrees C and 6 atm). Complexes 1-3 were also tested as precatalysts for the polymerization of propene. Interestingly, polymerization by 1-MAO at -20 degrees C afforded an isotactic polypropylene containing 5% isolated regioirregular units in threo configuration. This very unusual microstructure implicates that both primary and secondary monomer insertions occur with the same enantioface selectivity, at variance with what is observed in the case of metallocene catalysts. (c) 2006 Elsevier B.V All rights reserved.
引用
收藏
页码:275 / 283
页数:9
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