几种新的聚合物冠醚的合成及其络合与催化性能

由一、二、三和四缩乙二醇双钠盐与带有活泼卤原子的聚β-氯乙基缩水甘油醚进行环化反应,制备了四种新的聚合物冠醚(Ⅰ、Ⅱ、Ⅲ、Ⅳ)。络合容量测定结果表明,它们对K~+、Na~+均有较好的络合能力。在催化Wolff-Kishner(二苯甲酮腙还原为二苯甲烷)和正溴辛烷的碘代反应中,它们是有效的相转移催化剂。其中以Ⅱ最好,它的催化活性与小分子冠醚18-C-16和DB18-C-6相似,且易于回收,重复使用。

THE SYNTHESES OF SOME NEW POLYMERIC CROWN ETHERS WITH CATION-COMPLEXING AND CATALYTIC PROPERTIES

Four new polymeric crown ethers (Ⅰ, Ⅱ, Ⅲ, Ⅳ) were synthesized via direct cycli-zation of poly-β-chloroethyl glycidyl ether with disodium polyethylene glycolsH(OCH2·CH2)m OH, m=1, 2, 3,4]The cation-complexing ability and catalytic activity of these polymeric crown ethers have also been investigated. These polymers, especially polymer (Ⅱ) are effective phase transfer catalysts in Wolff-Kishner reaction, such as the formation of diphenylmethane from diphenylkctone hydrazone, and in the halogen exchange reaction i.e. the transformation of bromooctane to iodooctane by KI. The activity of polymer (Ⅱ) is comparable with that of dibenzo-18-crown-6 and 18-crown-6. These polymers can be easily recovered by simple filtration and reused. For Wolff-Kishner reaction the polymer (Ⅱ) could be reused twice without remarkable loss of activity. But in the case of the halogen exchange reaction, the recovered catalyst exhibited low activity.