Cai Zhengguo, Ohmagari Masayoshi, Nakayama Yuushou, Shiono Takeshi
Department of Applied Chemistry, Graduate School of Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan.
Macromol Rapid Commun. 2009 Nov 2;30(21):1812-6. doi: 10.1002/marc.200900413. Epub 2009 Sep 1.
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) ).
在甲苯中，以无三烷基铝的改性甲基铝氧烷（dMMAO）为助催化剂，通过[t-BuNSiMe(2) (3,6-t-Bu(2) Flu)]TiMe(2)（1）进行1-己烯聚合反应。该体系在0°C下能产生具有高链增长周转频率（TOF，98 s⁻¹）的活性间规聚（1-己烯）。链增长速率随1-己烯浓度呈线性增加，这表明链增长速率对单体浓度呈一级依赖性。还进行了1-辛烯、1-癸烯和1-十二碳烯的聚合反应，以通过该体系的活性研究1-烯烃链长对链增长速率的影响。链增长速率随链长增加而降低，直到1-癸烯，但在更长链的1-烯烃中几乎不变：TOF，1-辛烯（62 s⁻¹）>1-癸烯（32 s⁻¹）≈1-十二碳烯（31 s⁻¹）。
