Premium
Highly Active Syndiospecific Living Polymerization of Higher 1‐Alkene with ansa ‐Fluorenylamidodimethyltitanium Complex
Author(s) -
Cai Zhengguo,
Ohmagari Masayoshi,
Nakayama Yuushou,
Shiono Takeshi
Publication year - 2009
Publication title -
macromolecular rapid communications
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.348
H-Index - 154
eISSN - 1521-3927
pISSN - 1022-1336
DOI - 10.1002/marc.200900413
Subject(s) - methylaluminoxane , alkene , tacticity , polymerization , polymer chemistry , chemistry , living polymerization , radical polymerization , catalysis , polymer , organic chemistry , metallocene
1‐Hexene polymerization was conducted by [ t ‐BuNSiMe 2 (3,6‐ t ‐Bu 2 Flu)]TiMe 2 ( 1 ) using trialkylaluminum‐free modified methylaluminoxane (dMMAO) as a cocatalyst in toluene. The system produced living syndiotactic poly(1‐hexene) with high turnover frequency of propagation (TOF, 98 s −1 ) at 0 °C. The propagation rate was increased linearly against the 1‐hexene concentration, which indicates that the first‐order dependence of the propagation rate on monomer concentration. Polymerizations of 1‐octene, 1‐decene and 1‐dodecene were also conducted for investigating the effect of chain length of 1‐alkene on propagation rate by means of the livingness of this system. The propagation rate decreased according to the chain length until 1‐decene but almost unchanged in longer 1‐alkene: TOF, 1‐octene (62 s −1 )>1‐decene (32 s −1 ) ≈ 1‐dodecene (31 s −1 ).