新型后过渡金属配合物的合成及催化性能研究

Abstract

非茂型后过渡金属镍、钯催化剂具有良好的官能团耐受性，尤其是中性催化剂还可以实现单组分催化，这使得它们在烯烃均聚和共聚方面有着很好的应用前景。本论文合成了一系列 (硫)酚-膦(酰)中性镍、钯催化剂，并研究了他们对烯烃均聚和共聚的催化性能。主要内容如下： (1)为了研究[P,O]螯合中性镍催化剂对降冰片烯聚合的催化性能，我们设计合成了一系列酚-膦中性镍催化剂。它们在少量的B(C6F5)3(B/Ni = 3)活化下，可高效催化降冰片烯加成聚合，其中酚氧邻位为叔丁基的催化剂活性可达6.95 × 106 g/molNi?h。同时，这些催化剂还可单组分催化乙烯均聚，其中P上的两个取代基分别为叔丁基和苯基的催化剂活性高达1.07 × 107 g/molNi?h。在降冰片烯与乙烯共聚合实验中，降冰片烯插入率可超过30 mol%。 (2)为了探究酚-膦中性镍催化剂的共聚合性能及耐受性，我们选择了极性降冰片烯...Synthesis and study on Novel Late Transition Metal Catalysts for Olefin Polymerization Yanping Zhang(Polymer Chemistry and Physics) Directed by Professor Yuesheng Li Abstract Non-metallocene late metal (nickel and palladium) catalysts have great tolerance towards polar functional groups, and the neutral ones are even used as single component catalysts, which ensure their good application prospects in olefin (co)polymerization. In this thesis, we have synthesized a series of well-defined phosphine (oxide)-(thio) phenolate neutral nickel and palladium complexes for olefin homo- and copolymerization. The main contents are listed as follow: (1) To study the catalytic behavior of [P,O] chelate nickel catalysts for the vinyl-polymerization of norbornene, a series of phosphine-phenolate neutral n..