铁系亚胺基配合物催化乙烯齐聚表观动力学

Apparent Kinetics of Ethylene Oligomerization Catalyzed by Iron-Based 2,6-Bis(Im ino)Pyridyl Complexes

考察了4种具有电子效应差异的铁系亚胺基配合物2,6-二[(2-甲基-4-甲氧基-苯胺)乙基]吡啶二氯化铁、2,6-二[(2,4-二甲基-苯胺)乙基]吡啶二氯化铁、2,6-二[(2-甲基苯胺)乙基]吡啶二氯化铁和2,6-二[(2-甲基-4-溴-苯胺)乙基]吡啶二氯化铁,在不同反应温度、乙烯压力和催化剂用量下乙烯齐聚的表观动力学行为。在20～50℃、0 3～1 0MPa条件下,这4种配合物所制备催化剂的反应速率随反应温度升高、乙烯压力增大而提高,而随着催化剂浓度的增大,反应速率反而降低。利用简化的表观动力学方程,求出了催化剂的表观活化能和表观速率方程。

Apparent kinetics of ethylene oligomerization catalyzed by iron-based bis(imino)pyridyl complexes/MAO was investigated under 20～50 ℃,03～10 M Pa.Th e complexes were {2,6-bispyridine i ro n(II)chloride}(a),{2,6-bispyridine iron( 11 ) chloride}(b),{2,6-bispyridine iron(II) chlor id e}(c),and {2,6-bispyridine iron(II) ch loride}(d).Apparent kinetic parameters were determined.Apparent activation energies of cat alyst a,b,c,d were 30 kJ/mol,19 kJ/mol,13 kJ/mol,11 kJ/mol respectively.A pparent kinetic equations determination of catalyst a,b,c,d were R=36 ×105 ·e-3632/T-05p11,R=6003·e-23 16/T -05p11,R=812·e-1541/T  -054p10,R=493·e-1265/T -061p 12 respectively.