Immobilization of ferrocenecarboxylate on chloromethylated polymers

Abstract

Three chloromethylated polymers; chloromethylated polysulfone (POLYMER 1), poly (vinylbenzyl chlorideXPOLYMER 2), poly(vinylbenzyl chloride-fLQ.-2-ethoxyethyl methacrylate) (POLYMER 3) were prepared by bulk polymerization. The chloro- methyl group was converted to the ferrocenecarboxymethyl group by esterification with cesium ferrocenecarboxylate (CFC) using phase-transfer catalyst(PTC) in the liquid-liquid or solid- liquid two-phase systems. In these reactions, the effects of (a) reaction temperature, (b) mole ratio of CFC/-CH2CI in POLYMER 1, (c) amount of PTC, (d) types of PTCs, (e) stirring rate, (f) reaction systems, (g) solvent and (h) polymer structure on the degree of esteriflcation were investigated. The degree of esterification was found to increase with the increase in reaction temperature, in mole ratio of CFC/ -CH2CI in POLYMER 1, and also slightly with increase in stirring rate. The lower polarity of used solvent, the higher degree of esterification and uncross linked polymer can be obtained in the liquid-liquid two-phase reaction system. The catalytic activity of phase-transfer catalyst was found as follows; TBAC > TBPC > TBAB > TBAI > DCHC > TEAS. The optimum conditions for the synthesis of ferrocenecarboxymethylated poly¬mer bi the esterification reaction between POLYMER 1 and CFC using phase-tranfer catalyst are the reaction at 60°c, 200 rpm, used mole ratio of CFC/-CH2C1 in POLYMER 1/TBAC; 1.5/1/1, in' liquid-liquid two-phase system which chloroform is used as the solvent.