【作者】 杜建龙；

【导师】 李记太； 孙文华；

【作者基本信息】 河北大学 ， 有机化学， 2003， 硕士

【摘要】 后过渡金属催化剂是最近发展起来的一类高催化活性的非茂金属烯烃聚合催化体系。它在烯烃齐聚和聚合反应中的应用引起了学术界以及工业界极大的关注。 在前人研究工作的基础上，我们设计和合成了三个系列的含有氮、氮双齿，氮、氧、氮三齿配体的铁、钴和镍的配合物，并对其乙烯催化活性进行了研究。本论文主要分为四个部分： 第一部分：设计和合成了一系列2-（2′-吡啶基）苯并咪唑钴和镍的配合物。以这些配合物为催化剂，以MAO为助催化剂，在常温常压下进行了乙烯聚合研究，其中钴的配合物的催化活性在5.78×10³-7.50×10³gC₂H₄／molCo·h·atm，镍的配合物的催化活性在0.52×10⁵-1.14×10⁵gC₂H₄／molNi·h·atm，产物主要是C₄和C₆。 第二部分：设计和合成了一系列2-乙酰亚胺苯并咪唑铁、钴、镍的配合物。以这些配合物为催化剂，以MAO为助催化剂，进行了乙烯聚合研究，在常温常压下铁的配合物的催化活性在1.71×10⁴-2.01×10⁴gC₂H₄／molFe·h·atm，钴的配合物的催化活性在1.13×10⁴-1.75×10⁴gC₂H₄／molCo·h·atm，产物主要是C₄和C₆。对于镍的配合物，考察了温度以及[Al]／[Ni]对催化活性的影响，其催化活性在0.71×10⁵-2.58×10⁵gC₂H₄／molNi·h·atm，齐聚产物主要是C₄-C₂₀，并得到少量的聚合物，对聚合物的熔点、结晶度进行了分析。 第三部分：设计和合成了一系列对位甲基取代的水杨醛二亚胺钴的配合物。对配合物3的晶体进行了单晶衍射分析。以配合物为催化剂，以MAO为助催化剂，在常温常压下进行了乙烯聚合研究，考察了不同Al／Ni对催化活性的影响。其催化活性在1.14×10⁴-3.95×10⁴gC₂H₄／molNi·h·atm，产物主要是C₄和C₆。 第四部分：设计和合成了一系列对位叔丁基取代的水杨醛二亚胺钴和镍的配合物。以这些配合物为催化剂，以MAO为助催化剂，在常温常压下进行了乙烯聚合研究，其中钴的配合物的催化活性在1.78×10³-3.65×10³gC₂H₄／molCo·h·atm，镍的配合物的催化活性在1.98×10⁴-4.57×10⁴gC₂H₄／molNi·h·atm，产物主要是C₄和C₆。更多还原

【Abstract】 Olefin polymerization and oligomerization catalyzed by late transition metal complexes have attracted great attentions in both academic and industrial research. Late transition metal complexes are recently developed high active non-metallocene system.On the base of the investigation about the late transition metal catalysts, I designed and synthesized three novel series of iron, nickel and cobalt catalysts containting N, N or N, O, N ligands. My research work was mainly composed of four parts:In the first part, a series of new cobalt and nickel complexes L2M2X2 (M=Co or Ni, X=C1) bearing 2-(2-pyridyl)benzimidazole ligands(L) were synthesized. Treatment of the complexes L2M2X2 with methylaluminoxane(MAO) leads to active catalysts for oligomerization of ethylene with catalytic activities in the range of 5.78 103-7.50 103gC2H4/molCo-h-atm for Co complexes, and0.52 105-1.14 105gC2H4/molNi-h-atrn for the nickel complexes. The oligomers were olefins from C4 to C6.In the second part, a series of new nickel complexes LMX2 (M= Fe, Co or Ni, X=C1 or Br) bearing 2-acetylbis(imino)benzimidazole ligands(L) were synthesized. Treatment of the complexes LMX2 with methylaluminoxane(MAO) leads to active catalysts for oligomerization of ethylene with catalytic activities in the range of 1.13 104-2.01 104gC2H4/molM-h-atm for Iron and Cobalt complexes, The oligomers were olefins from C4 to C6. And catalytic activities are in the range of 0.71 105-2.58 105gC2H4/molNi-h-atm for the nickel complexes. The oligomers were olefins from C4 to C20- At the same time, some polyethylene was obtained.In the third part, a series of new cobalt complexes LMX2 (M=Co, X=C1) bearing 2,6-bis(imino)phenoxy ligands(L) were synthesized. The crystal structure of complex 3 has been determined by single-crystal X-ray diffraction study. Treatment of the complexes LMX2 with methylaluminoxane(MAO) leads to active catalysts for oligomerization of ethylene with catalytic activities in the range of 1.14 104-3.95 104gC2H4/molCo-h-atm for Co complexes. The oligomers were olefinsfrom C4 to C6.In the fourth part, a series of new cobalt and nickel complexes LMX2 (M=Co or Ni, X=C1) bearing 2,6-bis(imino)phenoxy ligands(L) were synthesized. Treatment of the complexes LMX2 with methylaluminoxane(MAO) leads to active catalysts for oligomerization of ethylene with catalytic activities in the range of 1.78 103-3.65 103gC2H4/molCo-h-atm for Co complexes, and1.98 104-4.57 104gC2H4/molNi-h-atm for the nickel complexes. The oligomers were olefins from C4 to C6.更多还原