Ko Young Soo, Lee Jeong Suk, Yim Jin-Heong, Jeon Jong-Ki, Jung Kyeong Youl
Department of Chemical Engineering, Kongju National University, Gongju, 314-701, Korea.
J Nanosci Nanotechnol. 2010 Jan;10(1):180-5. doi: 10.1166/jnn.2010.1536.
The effect of nanopore in mesoporous materials confining (n-BuCp),ZrCl2 and methylaluminoxane (MAO) on ethylene-1-hexene and ethylene-1-octene copolymerization was investigated on the basis of the copolymerization results, and the analysis of the supported catalyst and the copolymers. SBA-15 and MCM-41 together with amorphous silica were employed as supports, which are capable of confining (n-BuCp)2ZrCl2 and MAO in the nanopore. The copolymerization activities of MCM-41-supported (n-BuCp)2ZrCl2 were higher than those of SBA-15 and SiO2 although that its Zr content was quite lower than those of SBA-15 and SiO2. SBA-15 and MCM-41 showed a remarkable decrease in BET surface area after confining MAO and (n-BuCp)2ZrCl2 compared to SiO2, explaining an even adsorption of MAO and (n-BuCp)2ZrCl2 complexes on the nanopore surface. Temperature rising elution fractionation (TREF) results showed bimodal curves of MCM-41-supported (n-BuCp)2ZrCl2 at the C6/C2 and C8/C2 molar ratios of 0.6 and 0.5, respectively, which was attributed to the differences in ethylene and alpha-olefin concentrations along with the cylindrical nanopore of MCM-41 due to the narrow nanospace.
基于共聚结果以及对负载型催化剂和共聚物的分析，研究了介孔材料中纳米孔对（正丁基环戊二烯）二氯化锆（(n-BuCp)₂ZrCl₂）和甲基铝氧烷（MAO）在乙烯-1-己烯以及乙烯-1-辛烯共聚反应中的影响。采用SBA-15、MCM-41以及无定形二氧化硅作为载体，它们能够将(n-BuCp)₂ZrCl₂和MAO限制在纳米孔中。负载于MCM-41上的(n-BuCp)₂ZrCl₂的共聚活性高于负载于SBA-15和SiO₂上的，尽管其Zr含量远低于SBA-15和SiO₂的Zr含量。与SiO₂相比，SBA-15和MCM-41在负载MAO和(n-BuCp)₂ZrCl₂后BET表面积显著减小，这说明MAO和(n-BuCp)₂ZrCl₂配合物在纳米孔表面均匀吸附。升温淋洗分级（TREF）结果表明，负载于MCM-41上的(n-BuCp)₂ZrCl₂在C6/C2和C8/C2摩尔比分别为0.6和0.5时呈现双峰曲线，这归因于乙烯和α-烯烃浓度的差异以及由于纳米空间狭窄导致的MCM-41圆柱形纳米孔的影响。
