Department of Petroleum Chemistry and Organic Catalysis , Moscow State University , Moscow 119991 , Russia.
Topchiev Institute of Petrochemical Synthesis , Russian Academy of Sciences , Moscow 119991 , Russia.
ACS Appl Mater Interfaces. 2018 Aug 8;10(31):26566-26575. doi: 10.1021/acsami.8b02797. Epub 2018 Jul 24.
Anchoring Rh complexes to the surface of a silica polyamine composite, which has a poly(allylamine) covalently grafted to the surface of amorphous silica gel, yielded a material that proved to be an effective and novel heterogeneous catalyst for hydroformylation of unsaturated compounds. Surface amino groups of the material were modified with phosphines by covalent and ionic coupling. The modified materials were then treated with Rh(acac)(CO), giving the catalysts K-1 and K-2. Catalysts were characterized by solid-state NMR spectroscopy, IR spectroscopy, XPS, TEM, and elemental analysis. The activity and stability of K-1 and K-2 were then studied for the hydroformylation of selected unsaturated compounds. Hydroformylation of terminal double bonds occurred selectively in the presence of internal double bonds. Characterization of the catalysts and the problems encountered with the supported catalysts are discussed. Catalyst K-1 is reusable and can be applied to the hydroformylation of linear olefins, styrene, 4-vinylcyclohexene, and dienes, as well as representative terpenes and other unsaturated hydrocarbons in a batch reactor.
将 Rh 配合物锚定在硅烷多胺复合材料的表面上，该复合材料具有通过共价键接枝到无定形硅胶表面的聚(烯丙胺)，得到了一种被证明是用于不饱和化合物加氢甲酰化的有效且新颖的多相催化剂。材料的表面氨基通过共价和离子偶联与膦改性。然后用 Rh(acac)(CO)处理改性材料，得到催化剂 K-1 和 K-2。通过固态 NMR 光谱、IR 光谱、XPS、TEM 和元素分析对催化剂进行了表征。然后研究了 K-1 和 K-2 在选定的不饱和化合物加氢甲酰化中的活性和稳定性。在存在内部双键的情况下，末端双键的加氢甲酰化选择性发生。讨论了催化剂的表征和负载催化剂遇到的问题。催化剂 K-1 可重复使用，并可应用于在间歇反应器中进行线性烯烃、苯乙烯、4-乙烯基环己烯和二烯以及代表性萜烯和其他不饱和烃的加氢甲酰化。
