王俊,李昱颖,张娜,陈丽铎.超支化铬系催化剂的合成及乙烯齐聚性能研究[J].分子催化编辑部,2019,33(5):429-437
超支化铬系催化剂的合成及乙烯齐聚性能研究
Synthesis of Hyperbranched Chromium Catalysts and Study on Ethylene Oligomerization Properties
投稿时间:2019-07-23  修订日期:2019-08-30
DOI:
中文关键词:  超支化大分子  PNP铬系催化剂  乙烯齐聚  催化性能
英文关键词:hyperbranched macromolecule  PNP chromium catalyst  ethylene oligomerization  catalytic perfor-mance
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E-mail
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 wangjun1965@yeah.net 
李昱颖 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  
张娜 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  
陈丽铎 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:
      以正辛胺和十二胺为原料,分别制备了两种超支化PNP配体,通过引入金属铬活性位点的方法合成了具有不同烷基链长度的超支化PNP铬系催化剂.采用红外光谱(IR)、核磁共振磷谱(31P-NMR)、核磁共振氢谱(1H-NMR)、紫外光谱(UV)和质谱(MS)等表征方法证明合成催化剂的结构与理论结构预测相符.详细考察了催化剂用量、溶剂种类、反应条件以及配合物结构对乙烯齐聚性能的影响.实验结果显示,超支化PNP铬系催化剂在甲苯作溶剂,甲基铝氧烷(MAO)做助催化剂时表现出良好的催化乙烯齐聚性能,产物主要为低碳烯烃.在最佳条件下,催化活性最高可达到1.69×105 g·(mol Cr·h)-1,己烯和辛烯的选择性为43.3%以上.相同聚合条件下,其催化活性随着端基烷基链长度的增加而下降.
英文摘要:
      Two kinds of hyperbranched PNP ligands were prepared from n-octylamine and decylamine respectively. And the hyperbranched PNP chromium catalysts with different alkyl chain lengths were synthesized by introducing metal chromium active sites. A series of hyperbranched PNP chromium catalysts with different bridged alkyl chain lengths were synthesized by catalyst functionalizing the terminal amino groups using 1.0G hyperbranched macromolecules with different end alkyl chain lengths as bridged groups. IR,31P-NMR, 1H-NMR, UV and MS were used to prove that the structure of the synthesized catalyst was consistent with the theoretical structure. The effects of solvent dosage, solvent type, reaction conditions and complex structure on the oligomerization of ethylene were investigated in detail. The experimental results show that the hyperbranched PNP chromium catalyst exhibits good catalytic ethylene oligomerization performance, when the toluene is used as the solvent and the methylaluminoxane (MAO) is used as the promoter, and the product is mainly low-carbon olefin. The catalytic activity can reach up to 1.69×105 g·(mol Cr·h)-1. Under the optimum conditions, the selectivity of hexene and octene is above 43.3%. Under the same polymerization conditions, the catalytic activity decreased with the increase of terminal alkyl chain length.
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