Bibouche Bachir, Peral Daniel, Stehl Dmitrij, Söderholm Viktor, Schomäcker Reinhard, von Klitzing Regine, Vogt Dieter
Department of Chemistry, Technische Universität Berlin Straße des 17. Juni 124, TC-8 10623 Berlin Germany.
Department of Physics, Technische Universität Darmstadt Alarich-Weiss-Straße 10 64287 Darmstadt Germany.
RSC Adv. 2018 Jun 27;8(41):23332-23338. doi: 10.1039/c8ra04022b. eCollection 2018 Jun 21.
Micelle-like polymer particles have been applied in aqueous multiphasic hydroformylation reactions of long chain alkenes. These colloids act as phase transfer agents for the nonpolar substrates and as carriers for the catalyst bearing sulfonated ligands by electrostatic attraction. The catalyst performance and the phase separation were optimized with special focus on the conversion, selectivity and catalyst recovery, as those are key points in multiphasic systems to achieve a feasible industrial process. The effect on the catalyst performance of the number of sulfonate groups and electron withdrawing trifluoromethyl groups in the ligand has been studied. The approach was successfully demonstrated for 1-alkenes from 1-hexene to 1-dodecene. For 1-octene, a TOF of more than 3000 h could be achieved at a substrate to catalyst ratio of 80 000, while keeping the rhodium and phosphorous leaching below 1 ppm. In repetitive batch experiments the catalyst was recycled four times, yielding an accumulated TON of more than 100 000 for 1-octene.
胶束状聚合物颗粒已应用于长链烯烃的水相多相氢甲酰化反应中。这些胶体作为非极性底物的相转移剂，并通过静电吸引作用作为带有磺化配体的催化剂的载体。特别关注转化率、选择性和催化剂回收等方面，对催化剂性能和相分离进行了优化，因为这些是多相体系实现可行工业过程的关键点。研究了配体中磺酸根基团数量和吸电子三氟甲基对催化剂性能的影响。该方法已成功应用于从1-己烯到1-十二烯的1-烯烃。对于1-辛烯，在底物与催化剂的比例为80000时，可实现超过3000 h⁻¹的TOF，同时使铑和磷的浸出量低于1 ppm。在重复的间歇实验中，催化剂循环使用了四次，对于1-辛烯，累积TON超过100000。
