文章摘要
超支化PNP铬系催化剂的合成及对乙烯齐聚的催化性能
Synthesis and Catalytic Performance in Ethylene Oligomerization of Hyperbranched PNP Chromium Catalyst
  
DOI:10.16865/j.cnki.1000-7555.2018.08.004
中文关键词: 超支化大分子  PNP铬系催化剂  乙烯齐聚  催化活性
英文关键词: hyperbranched molecule  PNP chromium catalyst  ethylene oligomerization  catalytic activity
基金项目:国家重点研发计划资助(2017YFB0306701);国家自然科学基金资助项目(21576048)
作者单位
张 娜, 商益腾, 李翠勤, 施伟光, 王 俊 东北石油大学 化学化工学院 石油与天然气化工省重点实验室黑龙江 大庆 163318 
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中文摘要:
      以正己胺为核的1.0G超支化大分子(R6-1.0G)、氯代二苯基膦和CrCl3(THF)3为原料,合成了一种新型的超支化PNP铬系催化剂(R6-Cat)。红外光谱、核磁共振氢谱和紫外光谱证实合成产物的结构与理论结构相符。在合成的基础上,对该催化剂催化乙烯齐聚的性能进行了研究。考察了溶剂种类、反应温度、Al/Cr比、反应压力等条件对该催化剂催化乙烯齐聚性能的影响。结果表明,当以甲苯为溶剂,甲基铝氧烷(MAO)为助催化剂时,该催化剂表现出良好的催化乙烯齐聚性能。随着反应温度和Al/Cr比的增加,催化活性先升高后降低;而催化活性随着反应压力的增加而增大。当反应温度为35 ℃、Al/Cr比为500、反应压力为1.0 MPa时,催化活性可达2.02×104/sup>g/(mol Cr·h),聚合产物主要是C8以下的低碳烯烃,含量高达92%以上。相同条件下,其催化乙烯齐聚的活性高于与其结构类似但烷基链长度不同的超支化PNP铬系催化剂。
英文摘要:
      A novel hyperbranched PNP chromium catalyst was synthesized using the materials of 1.0G hyperbranched macromolecule with hexylamine as core, chlorodiphenylphosphine and CrCl3(THF)3. The structure of the hyperbranched PNP chromium catalyst was fully characterized by IR, 1H-NMR and UV. On the base of the synthesis of hyperbranched PNP chromium catalyst, the performance of ethylene oligomerization was investigated. The effects of the kind of solvent, reaction temperature, reaction pressure and Al/Cr ratio on catalytic performance in ethylene oligomerization were researched. The results show that the catalyst displays better catalytic performance in ethylene oligomerization with toluene as solvent and MAO as co-catalyst. The catalytic activity firstly increases and then decreases with the increase of reaction temperature and Al/Cr ratio. However, the catalytic activity increases with the increase of reaction pressure. The highest activity of 2.02×104/sup>g/(mol Cr·h) and 92% selectivity of less than C8 olefins are obtained under the conditions of the reaction temperature 35 ℃, the reaction pressure 1.0 MPa, and the Al/Cr ratio of 500. Under the same polymeric conditions, the catalytic activity of novel hyperbranched PNP chromium catalyst is better than the hyperbranched PNP chromium catalyst with a different length of alkyl chain in ethylene oligomerization.
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