有机高分子固载钯催化剂的羰基化和加氢催化性能

本文利用耐温性能较好的主链上含有多个配位原子(N，O)能成膜的直链高分子杂环联苯聚醚酮(PEK)，带酚酞侧基的聚醚砜(PES-C)和两种聚酰亚胺(PCK和PIK)为载体固载PdCl~2，制备了高分子固载钯催化剂。研究了它们在烯丙基溴的常压羰基化反应和1-辛烯的常压加氢反应中的催化性能。考察了催化剂的制备方法、Pd含量、溶剂和高分子的主链结构对催化剂活性的影响。催化剂Pd-PEK(Ⅰ) (Pd wt%=0.22%)和Pd-PES-C(Ⅱ)(Pd wt%=0.28%)在温和的条件下对上述两反应都表现出了很高的催化活性。在极低的Pd含量(Pd wt%=0.04%)时，催化剂Pd-PES-C(Ⅲ)显示出了特别高的初活性，TOF~m~a~x分别达345mol CO/mol Pd·min和493mol H~2/mol Pd·min。实验结果表明制备方法等因素对催化剂的活性有很大的影响。

Catalytic behaviors of the polymer-supported palladium catalysts for hydrogenation and carbonylation

The organic polymer-supported catalysts were prepared by refluxing the mixture of poly(heterocyclic ether-ketone) (PEK), phenophthalein poly(ether sulfone) (PES-C), and two kinds of polyimides (PCK and PIK) with coordinating atoms (N, O) in their functional chains and PdCl~2 in ethanol/benzene, respectively. The carbonylation of allyl bromide and hydrogenation of 1-octene were carried out under atmospheric pressure and at 40℃. Among these catalysts, Pd-PEK(Ⅰ) (Pd wt%=0.22%) and Pd-PES-C(Ⅱ)(Pd wt%=0.28%) showed high catalytic activity to the carbonylation and hydrogenation. In particular, the catalysts Pd-PES-C with very low Pd content (0.04～0.05 wt%) also exhibited very high activity (TOF~m~a~x, 345mol CO/mol Pd·min and 493mol H~2/mol Pd·min). The influences of the preparation methods for the catalysts, the swelling effect and the functional chains of the polymers on the catalyst activities were also discussed.