不对称PNP配体的合成及其在乙烯选择性齐聚中的应用  

Synthesis of unsymmetrical PNP ligands and their application in selective oligomerization of ethylene

作　　者：胡嵩霜 吴红飞 胡超杰[3] 赵兴 张军 HU Song-shuang;WU Hong-fei;HU Chao-jie;ZHAO Xing;ZHANG Jun(Yanshan Branch,Sinopec Beijing Research Institute of Chemical Industry,Beijing 102500,China;National Engineering Research Center for Synthesis of Novel Rubber and Plastic Materials,Beijing 102500,China;School of Chemistry and Molecular Engineering,East China University of Science and Technology,Shanghai 200237,China)

机构地区：[1]中石化(北京)化工研究院有限公司燕山分公司,北京102500 [2]橡塑新型材料合成国家工程研究中心,北京102500 [3]华东理工大学化学与分子工程学院,上海200237

出　　处：《现代化工》2025年第4期229-233,共5页Modern Chemical Industry

摘　　要：设计、合成了一类磷原子上含间位和对位取代芳基的不对称PNP配体Ph_(2)PN(~iPr)Ar_(2),并将其用于铬催化的乙烯选择性聚合反应中。结果表明,在60℃和4 MPa乙烯压力下,经MMAO-3A助催化剂活化后,配体L~1(Ph_(2)PN(~iPr)PAr_(2),Ar=m-CH_(3)C_(6)H_(4))表现出较经典PNP配体[(Ph_(2)P)_(2)N-~iPr]更好的催化性能,催化活性较高为1370 kg/(gCr·h)、1-辛烯选择性为68.9%及1-己烯和1-辛烯综合选择性为85.0%。此外,还考察了磷原子上间位取代苯基的电子效应对这类配体催化性能的影响。A series of unasymmetrical PNP ligands,which contain meta-and para-substituted aryl groups on their P atoms,are synthesized,and applied in the selective ethylene oligomerization that is catalyzed by chromium catalyst.It is found that upon activation with modified methylalumoxane(MMAO-3A)and at 60℃,40 bar ethylene pressure,ligand L 1(Ph_(2)PN(i Pr)PAr_(2),Ar=m-CH_(3)C_(6)H_(4))exhibits much better catalytic performance than previously reported PNP ligand(Ph_(2)PN(i Pr)PPh_(2)),achieving a high catalytic activity of 1370 kg/(gCr·h),a high 1-octene selectivity of 68.9 wt.%and a considerable total 1-hexene/1-octene selectivity of 85.0 wt.%.Moreover,the impact of electronic effect of different meta-substituted phenyl group on P atoms on the catalytic performance of such ligands is also explored.

关 键 词：PNP配体 铬系催化剂 乙烯 选择性聚合 

分 类 号：TQ426.92[化学工程]