负载型茂金属催化剂催化乙烯淤浆聚合
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聚烯烃催化技术与高性能材料国家重点实验室

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TQ325.1

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广西科技重大专项


Preparation and catalytic performance of supported metallocene catalysts for ethylene slurry polymerization
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State Key Laboratory of Polyolefins and Catalysis

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Guangxi Science and Technology Major Project

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    摘要:

    以聚甲基铝氧烷(MAO)、双(正丁基环戊二烯基)二氯化锆为金属源,活化硅胶为载体,制备了两种不同铝锆含量的硅胶负载茂金属催化剂cat1和cat2,采用FTIR、激光粒度仪、电感耦合等离子体发射光谱仪(ICP-OES)等表征cat1和cat2的化学组成、粒径分布。利用淤浆聚合考察了聚合温度、聚合时间对催化剂催化活性和聚乙烯黏均分子量(Mv)的影响,并采用DSC和流变分析法对催化制备的聚乙烯进行了缠结度表征。结果表明,高金属负载cat1的Al、Zr质量分数分别为21.26%、0.70%,低金属负载cat2的Al、Zr质量分数分别为7.37%、0.20%。不同金属负载的cat1和cat2催化乙烯聚合动力学有显著差异,在聚合温度为70和60 ℃时,cat1、cat2催化乙烯聚合活性分别达到9200、5140 g(PE)/g(cat),制备的聚乙烯的Mv分别为3.20×105、3.70×105 g/mol;cat1催化乙烯活性较为平稳,催化剂寿命长(8 h),整体活性较高;cat2制备的低Mv树脂具有明显的解缠结特性。同时,树脂的缠结度随着Mv的增加而增大。

    Abstract:

    Two types of silica gel supported metallocene catalysts, cat1 and cat2, with different aluminum zirconium contents, were prepared using polymethylaluminoxane (MAO) and bis (n-butylcyclopentadienyl) zirconium dichloride as metal sources and activated silica gel as carriers. The chemical composition and particle size distribution of cat1 and cat2 were characterized using FTIR, laser particle size analyzer, inductively coupled plasma emission spectroscopy (ICP-OES), and other methods. The effects of polymerization temperature and time on the catalytic activity and viscosity average molecular weight (Mv) of polyethylene were investigated using slurry polymerization, and the entanglement degree of polyethylene prepared by catalysts was characterized using DSC and rheological analysis. The results showed that the Al and Zr mass fractions of high metal loading cat1 were 21.26% and 0.70%, and the Al and Zr mass fractions of low metal loading cat2 were 7.37% and 0.20%. There were significant differences in the kinetics of catalytic ethylene polymerisation between cat1 and cat2 with different metal loadings. At polymerization temperatures of 70 and 60 ℃, the catalytic activity of cat1 and cat2 for ethylene polymerization reached 9200 and 5140 g (PE)/g (cat), respectively. The Mv of the prepared polyethylene was 3.20×105 and 3.70×105 g/mol, respectively; cat1 had relatively stable catalytic activity for ethylene, long catalyst life (8 hours), and overall high activity; The low Mv resin prepared by cat2 exhibited significant entanglement removal properties. Meanwhile, the entanglement degree of the resin increased with the increase of Mv.

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花紫阳,郭建双,李建龙,赖春波,李雪坤.负载型茂金属催化剂催化乙烯淤浆聚合[J].精细化工,2025,42(3):

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  • 收稿日期:2024-02-08
  • 最后修改日期:2024-04-26
  • 录用日期:2024-04-07
  • 在线发布日期: 2025-03-14
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