担载型水溶性膦铑配合物催化剂研究

烯类氢甲酰化反应包括了均相催化的某些重要应用。含贵金属和贵重配体的均相催化剂与产物的分离及制备高活性、高选择性、高稳定性催化剂,是均相催化及其多相化最活跃的研究领域之一。对于氢甲酰化催化剂多相化,在基础研究和技术上都仍存在如何解决好催化活性、反应选择性变化或金属流失等问题。将HRh(CO)[P(m-C_6H_4SO_33Na)_3]_3担载在亲水性

Studies on Supported-Water-Soluble Phosphine Rhodium Complex Catalyst

Much attention has been paid to the heterogenization of homogeneous rhodium complexes responsible for olefine hydroformylation catalysts in the literature. Many methods have been proposed, but no heterogeneous hydroformylation catalysts are commercially used so far for liquid-phase conversion, primarily because of problems arising from catalyst loss to the product-containing phase. The supported water-soluble phosphine-rhodium complex has been designed to facilitate hydroformylation at interface of two liquids. Immobilization of the catalyst is accomplished by means of the insolubility of the rhodium complex in the organic media. SiO2 supported water-soluble sulfonated-triphenylphos-phine-rhodium complex shows an excellent catalytic activity for the hydroformylation of higher olefine of methyl 10-undeceoate. The reaction can be easily carried out in a fixed bed reaction system and it is found that the selectivity stabilized in the range of 98%-99% and n-/iso- ratios over 4. 0 when P/ Rh molecular ratios in 10-15 under the testing period. This immobilized catalyst also shows significant water loss during the reaction based on IR data of the catalyst, but non-effect on the catalytic activity has been observed. It is proposed that the ligands and central metal may be redistributed at the initial stage of the reaction to form active species with suitable water content in the fresh catalyst, and then the hydrophilic support holds the water-soluble phosphines by hydrogen bonding of the hydrated sodium-sulfonate group of the surface.