α-二亚胺镍钯配合物合成及催化混合癸烯低聚研究  

Synthesis and Catalytic Performance ofα-Diimine Nickel and Palladium Complexes for Oligomerization of Decene Mixture

作　　者：阮晶晶 郑涵斗 蒋岩 王力搏 王斯晗 高海洋 Jing-jing Ruan;Han-dou Zheng;Yan Jiang;Li-bo Wang;Si-han Wang;Hai-yang Gao(School of Materials Science and Engineering,Key Laboratory of Polymer Composites&Functional Materials of Ministry of Education,Sun Yat-sen University,Guangzhou 510006;Daqing Chemical Engineering Research Center,Petrochemical Research Institute,China National Petroleum Corporation,Daqing 163714)

机构地区：[1]聚合物复合材料及功能材料教育部重点实验室,中山大学材料科学与工程学院,广州510006 [2]中国石油石油化工研究院大庆化工研究中心,大庆163714

出　　处：《高分子学报》2021年第12期1603-1610,I0004,共9页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号51873234);广东省基础与应用基础研究基金(基金号2019B1515120063);中国石油资助项目(项目号DQZX-KY-21-012)资助.

摘　　要：α-二亚胺镍钯催化剂具有独特的链行走的特点,通过对催化剂结构设计可以进一步调控其催化性能和链行走过程来制备性能优异的聚烯烃产品.本文合成和表征了莰基骨架的α-二亚胺镍钯配合物,并研究了其在一氯二乙基铝的助催化作用下催化混合癸烯低聚性能.详细探究了催化剂金属中心、溶剂、温度及铝镍比对混合癸烯低聚结果的影响.钯催化剂催化混合癸烯低聚时几乎无活性;而镍催化剂具有较好的催化活性,结合单体的异构化过程线性的单体几乎能完全低聚转化.所得到的产物是高度支化、低分子量的油状聚烯烃产物,并且具有高的黏度指数(>170),低的倾点(<-30℃),在润滑油基础油领域具有良好应用前景.α-Diimine nickel and palladium catalysts catalyze olefins polymerization to form branched products because of unique chain walking characteristics.Design and optimization of catalyst ligand structure can control its catalytic properties and chain walking process,thereby developing high-performance polyolefins.In this paper,newα-diimine nickel and palladium complexes with a rigid camphyl backbone were designed and synthesized for oligomerization of decene mixture.X-ray single crystal diffraction patterns of nickel(Ni-1)and palladium(Pd-1)complexes clearly proved molecular structure of nickel and palladium complexes.The buried volume of nickel and palladium complexes calculated by single crystal structure data supported the bulky steric effect of the camphyl backbone.The influence of metal center,solvent,temperature and Al/Ni ratio on oligomerization of decene mixture were studied in detail.Palladium-based catalyst was nearly inactive but nickel-based catalyst showed good activity toward oligomerization of decene mixture.In combination with isomerization of nonterminal olefins,linear components of decene mixture were nearly converted to oligomers.The resultant polyolefins were highly branched(branching degree>120/1000C)and had low molecular weight(3100‒4540 g/mol).The lubricant properties of the resultant oil products were further evaluated according to Chinese national standard.These polyolefin oils had excellent properties of viscosity index higher than 170 and pour point lower than-30°C,showing a good potential in the field of polyolefin lubricant base oil.

关 键 词：镍钯催化剂 烯烃 低聚 支化 

分 类 号：O643.36[理学—物理化学] O641.4[理学—化学]