新型氧钒配合物的合成及催化乙烯(共)聚合活性研究  

Novel Oxo-vanadium Complexes:Synthesis and Study on Catalytic Properties for Ethylene(Co)Polymerization

作　　者：刘金海 赖新鑫 任丽 郝俊鹏 李小英 吴玥莹 卢令攀 LIU Jin-hai;LAI Xin-xin;REN Li;HAO Jun-peng;LI Xiao-ying;WU Yue-ying;LU Ling-pan(a.Henan Engineering Research Center of Water Environment and Health,Zhengzhou University of Industrial Technology,Zhengzhou 451100,China;School of Pharmacy and Chemical Engineering,Zhengzhou University of Industrial Technology,Zhengzhou 451100,China)

机构地区：[1]郑州工业应用技术学院河南省水环境与健康工程技术研究中心,河南郑州451100 [2]郑州工业应用技术学院药学与化学工程学院,河南郑州451100

出　　处：《化学试剂》2024年第1期98-104,共7页Chemical Reagents

基　　金：河南省科技攻关项目(232102310391);河南省高等学校重点科研项目(23B350002);郑州工业应用技术学院博士科研启动基金项目(2018B033)。

摘　　要：烯烃和功能化单体共聚合是制备功能化聚烯烃的重要途径之一。在催化烯烃和功能化单体共聚合过程中,钒系过渡金属催化剂的失活是目前最具挑战的问题。为发现热稳定性好、极性单体耐受性优良的新型钒系催化剂,设计并合成了[NOON]型多齿配体螯合的6,6′-((2-(二甲胺基)乙基)氮甲双基)双(2-甲氧基-4-甲基苯酚)(2a)和6,6′-((2-(吡啶-2-基)乙基)氮甲双基)双(2-甲氧基-4-甲基苯酚)(2b),并通过^(1)HNMR、^(13)CNMR、^(51)VNMR以及XRD的方法确认分子结构。乙烯均聚结果表明,两种钒配合物均能在高温下高活性催化乙烯聚合(活性最高达40.2 kg/mmol V·h),表现出良好的热稳定性。在乙烯与5-降冰片烯-2-甲醇共聚合中,两种钒配合物同样表现出较高活性,极性单体插入率最高可达1.66%。Copolymerization of olefin and functional monomer is one of the important ways to prepare functional polyolefin.The deactivation of vanadium transition metal catalysts is the most challenging problem in the copolymerization of olefin and functional monomers.In order to find novel vanadium catalysts with good thermal stability and excellent tolerance to polar monomers,designed and synthesized 6,6′-((2-(dimethylamino)ethyl)nitromethylbis)bis(2-methoxy-4-methylphenol)(2a)and 6,6′-((2-(pyridin-2-yl)ethyl)nitromethylbis)bis(2-methoxy-4-methylphenol)(2b)chelated with[NOON]type multi dentate ligands.The molecular structures were confirmed by ^(1)HNMR,^(13)CNMR,^(51)VNMR and X-ray single crystal diffraction.The results of ethylene homopolymerization show that two types of vanadium complexes exhibited high activity at high temperature(up to 40.2 kg/mmol V·h),displaying good thermal stability.In the copolymerization of ethylene with 5-norbornene-2-methanol,two types of vanadium complexes also showed high activity,and the insertion rate of polar monomer was up to 1.66%.

关 键 词：多齿配体 氧钒配合物 极性单体 乙烯均聚合 共聚合 

分 类 号：O62[理学—有机化学]