有机高分子固载钯催化剂的羰基化和加氢催化性能  

Catalytic Behaviors of the Polymer - supported Palladium Catalysts for Hydrogenation and Carbonylation

作　　者：余正坤[1] 徐筠[1] 廖世健[1] 余道容[1] 杨少华[1] 赵永魁[2] 范荫恒[2] 蹇锡高[3] 孟跃中[3] 

机构地区：[1]中国科学院大连化学物理研究所,大连116023 [2]辽宁师范大学化学系,大连116022 [3]大连理工大学化工学院,大连116012

出　　处：《化学学报》1996年第3期253-260,共8页Acta Chimica Sinica

基　　金：国家自然科学基金;中国科学院上海有机化学研究所金属有机开放实验室资助项目

摘　　要：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,制备了高分子固载的钯催化剂.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_(max)分别达345molCO/molPd·min和493molH_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.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 PdCl2 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 (TOFmax, 345 molCO/molPd ?min and 493 molH2/molPd ?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 dicussed.

关 键 词：钯 催化剂 羰基化反应 加反应 催化剂活性 

分 类 号：O641.361[理学—物理化学]