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研制了以交联苯乙烯—二乙烯基苯共聚物为载体的含氮功能团的固载铑络合物催化剂,得到两种活性较好的螯合型固载铑催化剂,用于醋酸甲酯羰基化制醋酐,其活性均略高于它们相应的均相类似体系。XPS测定表明,固载铑催化剂形成强的N→Rh键,且N/Rh=15时其活性最好。在418～447K范围测得醋酐生成平均速率与温度的关系,求得的表观活化参数(E_a=73.3KJ/mol,△H~≠=66.3KJ/mol,△S~≠=-28.6eu),表明氧化加成参与速控步骤。适当比例的溶剂醋酸对固载铑催化剂高活性是必须的。
A rhodium complex catalyst containing nitrogen functional groups with a cross-linked styrene-divinylbenzene copolymer as a carrier was prepared. Two chelating rhodium-supported catalysts with good activity were obtained and used for methyl acetate Carbonylation of acetic anhydride, its activity were slightly higher than their corresponding homogeneous similar system. The results of XPS showed that the immobilized rhodium catalyst formed a strong N → Rh bond and its activity was the best when N / Rh = 15. The relationship between the average rate of acetic anhydride formation and temperature was measured in the range of 418 ~ 447K. The apparent activation parameters (E_a = 73.3KJ / mol, △ H ~ ≠ = 66.3KJ / mol, △ S ~ ≠ = -28.6eu ), Indicating that the oxidation addition is involved in the quick control step. An appropriate ratio of solvent acetic acid to rhodium-supported catalyst is necessary.