Molecules. 2019 Apr 13;24(8):1467. doi: 10.3390/molecules24081467.
Silica generated from agricultural waste is more cost effective and environmentally friendly than silica from traditional commercial processes. In this study, spherical silica particles with a diameter of around 120 nm were fabricated from rice husk ash (RHA), and were used to support two bridged zirconcene complexes ((I) MeSi(Ind)ZrCl and (II) CH(Ind)ZrCl ) for catalyzing propylene polymerization to produce polypropylene (PP) in a temperature range of 40-70 C and in a solution methylaluminoxane (MAO) range of 0.1-0.6 wt%. Due to its small particle size, RHA-supported catalyst exhibited much higher activity than micro-sized commercial silica-supported catalyst. At the optimum polymerization temperature of 55 C and with increasing MAO concentration, polymer yield increased proportionally with the increase of number average molecular weight. Compared to (I), (II) produced more polymer molecules but with much shorter chain length, ascribed to the differences of Zr loading and bridge structure. With increasing polymerization temperature, polymer molecular weight decreased rapidly and resulted in a significant change of PP assembly morphology (shape and size). At 55 C, (I) produced uniform PP assemblies which had dumbbell-like structure with a smooth middle section and two fibrillar ends, while (II) produced spherical PP particles. The dumbbell middle part width was essentially identical to the Batchelor microscale proposed in turbulent mixing theory.
从农业废料中生成的硅石比传统商业工艺中的硅石更具成本效益和环保性。在这项研究中,我们使用稻壳灰(RHA)制造出了直径约为 120nm 的球形硅石颗粒,并将其用于支撑两种桥联锆络合物((I)MeSi(Ind)ZrCl 和(II)CH(Ind)ZrCl),以催化丙烯聚合,在 40-70°C 的温度范围内和 0.1-0.6wt%的甲基铝氧烷(MAO)范围内生产聚丙烯(PP)。由于其粒径较小,RHA 负载的催化剂的活性比微尺寸商业硅石负载的催化剂高得多。在最佳聚合温度为 55°C 时,随着 MAO 浓度的增加,聚合物产率与数均分子量的增加成正比。与(I)相比,(II)产生了更多的聚合物分子,但链长短得多,这归因于 Zr 负载量和桥接结构的差异。随着聚合温度的升高,聚合物的分子量迅速降低,导致 PP 组装形态(形状和尺寸)发生显著变化。在 55°C 时,(I)产生了均匀的 PP 组装体,其具有哑铃状结构,中间部分光滑,两端呈纤维状,而(II)则产生了球形 PP 颗粒。哑铃中间部分的宽度与湍流混合理论中提出的 Batchelor 微尺度基本相同。