Synthesis and phase‐transfer catalytic activity of hydroxyl‐containing polyetheramines bound to soluble or insoluble polystyrenes

Abstract

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.

Solvent and Reagent Accessibility within Oligo(ethylene glycol) Ether [PEG] Cross-Linked Polystyrene Beads

“…Our interest in solid-phase synthesis, support modification, and cross-link functionalization prompted us to investigate the properties of oligo(ethylene glycol) cross-linked PS beads. Poly(ethylene glycol) [PEG], introduced via grafting to chloromethylated PS−DVB, has been shown to increase swelling in polar solvents, and several PEG-grafted PS−DVB supports have emerged (cf., TentaGel and ArgoGel) based on the work of Inman, Regen, Mutter, Bayer and Rapp, Barany, and others . A drawback of the grafting approach, however, is that it reduces the functional group-to-mass ratio (polymer loading) by decreasing the number of free chloromethyl groups while increasing the resin mass.…”