Soluble polystyrenes with crown ether structures and hydroxyl groups adjacent to the macrorings were prepared by the reaction of epoxide‐containing polystyrenes with monoaza‐15‐crown‐5 or monoaza‐18‐crown‐6. Rate of formation of the polymer‐bound alkali cation‐crown alkoxide ion pair from the soluble polystyrenes and aqueous NaOH or KOH depended on the loading of crown ether and hydroxyl units and on the size of the macroring. The elimination of HCl from less reactive 2‐chloroethylbenzene with aqueous NaOH or KOH in the presence of the soluble polystyrene catalysts under two‐phase conditions was limited mainly by the intrinsic reaction rate. The elimination of HBr from more reactive 2‐bromoethylbenzene in the presence of the less (11%) ring‐substituted polymer catalyst with 18‐crown unit was limited by the alkoxide formation rate. © 1994 John Wiley & Sons, Inc.

Soluble or insoluble polystyrenes with hydroxyl-containing polyetheramine structures were prepared by the reaction of linear or crosslinked polystyrenes containing haloalkyl, tosyloxyalkyl, or epoxy groups with bis(2-(2-hydroxyethoxy)ethyl)amine (ATEG). The soluble polystyrenes with ATEG residue afforded polymeric alkoxides by the reaction with aqueous NaOH or KOH under two-phase conditions. The introduction of oxygen-containing spacer chains between ATEG residue and the polymer backbone resulted in the formation of cryptand-like alkoxides, in which the counter cations were bound by cooperative coordination of the oxygen donors in the ATEG residue and in the spacers. The soluble and insoluble polymers with ATEG residue exhibited high catalytic activity for the dehydrobromination of 2-bromoethylbenzene with aqueous NaOH or KOH under two-and three-phase conditions, respectively. The extra coordination of the oxygen donors in the spacers resulted in increased catalytic activity.