Synthesis and characterization of Styrene and Acrylate-based polymer-supported reagents

The synthesis and characterization of dual mechanism bifunctional polymers (DMBPs) were accomplished. Class II (ion exchange/coordination) DMBPs based on phosphonic acid esters were synthesized and their preparation conditions were studied.

Complexation of series of substituted anilines and benzoic acids were investigated using phosphinic acid functionalized polystyrene and dimethylamine functionalized poly(vinylbenzyl chloride) resins. The strength of interaction between substrates and polymeric ligands was quantified in terms of binding constants and useful information were obtained by evaluating the binding constants through Hammett-type free energy relationship.

As an alternative to polystyrene-based supports, poly(glycidyl methacrylate) (poly(GMA)) resins with increased hydrophilicity and relatively good hydrolytic stability were synthesized and characterized. The epoxide group as the precursor was proposed for coordinating ligands in bifunctional ion exchange/coordination polymers due to its susceptibility to nucleophilic attack.

Polymer-supported methyl azodicarboxylate polystyrene resins used in Mitsunobu esterification reactions were prepared. Limited Hammett studies on substituted benzoic acids showed a clear trend in the extent of esterification as a function of electron donating or withdrawing ability of the substituents on the substrate.