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本文考察了不同氯化物对铑膦络合物催化丙烯氢甲酰化反应速度的影响及其作用规律,追踪了铑膦络合物结构变化的过程,检测出无催化活性的铑氯络合物的红外结构数据,提出铑膦络合催化剂的氯致失活机理并加以实验论证及理论分析。研究了HCl、Cl_2、CH_2Cl_2、CHCl_3、CCl_4及1,2—C_2H_4Cl_2等小分子含氯化合物对反应速度的影响及其作用规律,并对氯仿的中毒作用进行了重点研究。实验证明,在100℃,16atmg总压下,各种氯化物的毒性强弱顺序为。 HCl>Cl_2>CCl_4>CHCl_3>CH_2Cl_2>1,2—C_2H_4Cl_2,导致催化剂完全失活所需的氯铑比分别为: HCl/Rh=2,Cl_2/Rh=13;CHCl_3/Rh=900失活的原因在于氯化物直接和铑络合物的催化活性组份发生氧化加成作用,并生成无催化活性的铑氯络合物,然后再进一步使之转化为多氯铑络合物或铑氯化合物。四氯化碳除了能直接和铑膦络合催化剂作用外,还不可逆地破坏三苯基膦配位体的结构。
In this paper, the effects of different chlorides on the catalytic rate of propane hydroformylation catalyzed by rhodium-phosphine complexes were investigated. The changes of the structure of rhodium-phosphine complexes were traced. The catalytic activity of rhodium-chloride complexes The structure of rhodium phosphine catalyst was proposed and the mechanism of chlorine induced deactivation was proposed. The experimental evidence and theoretical analysis were also given. The effects of HCl, Cl_2, CH_2Cl_2, CHCl_3, CCl_4 and 1,2-C_2H_4Cl_2 on the reaction rate and their action laws were studied. The toxic effects of chloroform were also studied. Experiments show that at 100 ℃, 16atmg total pressure, the toxicity of various chloride order. HCl / Cl 2> CCl 4> CHCl 3> CH 2 Cl 2> 1, 2-C 2 H 4 Cl 2, resulting in complete deactivation of the catalyst required for the ratio of HCl to Rh = 2, Cl 2 / Rh = 13; CHCl 3 / Rh = 900 inactivated The reason is that the chloride directly undergoes an oxidative addition reaction with the catalytically active component of the rhodium complex and forms a catalytically inactive rhodium chloride complex which is then further converted into a polychlorinated rhodium complex or a rhodium chloride compound . Carbon tetrachloride irreversibly disrupts the structure of the triphenylphosphine ligand in addition to acting directly on the rhodium phosphine complex catalyst.