Journal of Polymer Science · 1959 · 57 citations · 3 references
Ethylene GlycolChemical KineticsEngineeringOrganic ChemistryPolyesterification ReactionsChemistryForeign AcidPolymersChemical EngineeringHydrogen Ion CatalysisHomogeneous CatalysisPolymer ChemistryBiocatalysisCatalysisDibasic AcidsCatalytic SynthesisNatural SciencesMolecular CatalysisPolymer ReactionPolymer Synthesis
Abstract On the basis of our experimental data and a detailed kinetic analysis, the following mechanism of hydrogen ion catalysis is proposed for polyesterification as well as for the simple esterification reactions: magnified image The kinetic equation in terms of [COOH] (= C ) is where C 0 = [COOH] and r = [COOH]/[OH] at the time t = 0. All of our data on the polyesterification of succinic acid or adipic acid with ethylene glycol at various molar ratios and at different temperatures, in the presence or absence of a foreign acid, support the above equation. For the special case of r = 1 and in the absenc of a foreign acid, ([H + ] = K [COOH] 1/2 ), and polyesterification is hence shown to be a reaction of an order of 2.5. The data of Dostal and Raff, Flory, Davies, and Rafikov and Korshak, have been re‐examined and found to conform to the 2.5‐order relationship over the range of 0 to 92% polyesterification.
3