Olefin Polymerization by Half-Titanocenes Containing η2-Pyrazolato Ligands-MAO Catalyst Systems

被引:30
作者
Nomura, Kotohiro [1 ,2 ]
Fukuda, Hiroya [2 ]
Katao, Shohei [2 ]
Fujiki, Michiya [2 ]
Kim, Hyun Joon [3 ]
Kim, Dong-Hyun [3 ]
Saeed, Irfan [2 ]
机构
[1] Tokyo Metropolitan Univ, Dept Chem, Tokyo 1920397, Japan
[2] Nara Inst Sci & Technol, Grad Sch Mat Sci, Nara 6300101, Japan
[3] Korea Inst Ind Technol, Cheonan Si 331825, Chungnam, South Korea
基金
日本学术振兴会;
关键词
ETHYLENE-NORBORNENE COPOLYMERS; ANSA-FLUORENYLAMIDODIMETHYLTITANIUM COMPLEX; SYNDIOSPECIFIC STYRENE POLYMERIZATION; ANCILLARY DONOR LIGANDS; (CYCLOPENTADIENYL)(ARYLOXY)TITANIUM(IV) COMPLEXES; STRUCTURAL-ANALYSIS; ETHYLENE/NORBORNENE COPOLYMERIZATION; LIVING COPOLYMERIZATION; METALLOCENE COMPLEXES; ALKENE POLYMERIZATION;
D O I
10.1021/ma200018z
中图分类号
O63 [高分子化学(高聚物)];
学科分类号
070305 ; 080501 ; 081704 ;
摘要
A series of half-titanocenes containing pyrazolato ligands, Cp'TiCl2(3,5-R2C3HN2) (1a-d, 2a-c, 3a-c) [Cp' = Cp (1), Cp+ (2), tert-BuC5H4 (tert-BuCp, 3); R = H (a), Me (b), Pr-i (c), Ph (d)], have been employed as the catalyst precursors for ethylene polymerization, syndiospecific styrene polymerization, and copolymerization of ethylene with 1-hexene, styrene, and norbornene (NBE) in the presence of MAO cocatalyst. The Cp* analogues, especially 2a,b, exhibited high catalytic activities for ethylene polymerization affording the polymer with unimodal molecular weight distributions, whereas the Cp analogue (especially 1b,c) and the tert-BuCp analogues (3a-c) exhibited high catalytic activities for syndiospecific styrene polymerization. The ethylene/styrene copolymerization using the tert-BuCp diisopropyl analogue (3c) -MAO catalyst system proceeds in a living manner, irrespective of the styrene concentration employed (in toluene at 25 degrees C), and the same system exhibited relatively high catalytic activity for the ethylene/NBE copolymerization with highly efficient NBE incorporation.
引用
收藏
页码:1986 / 1998
页数:13
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