New terpolymers from n-butyl acrylate, glycidyl methacrylate and tetrahydrofurfuryl acrylate: Synthesis, characterisation and estimation of reactivity ratios

Abstract

Development and practical application of multicomponent copolymerisation systems, such as terpolymerisation, is an on-going process because even a small addition of a particular comonomer may have a significant impact on the desired property. Commonly, three separate pairs of binary polymerisation experiments are carried out to obtain monomer reactivity ratios (MRR) values that relates to the ternary polymerisation reactions. However, the reaction conditions in each binary system may not be representative of the whole ternary system. The error-in-variables model (EVM) method is a relatively recent statistical approach to solving multi-response parameter estimation problems, with the advantage that all MRR parameters can be directly estimated from terpolymerisation data. New ternary copolymers derived from n-butyl acrylate (nBA), glycidyl methacrylate (GMA) and tetrahydrofurfuryl acrylate (THFA) were synthesised in solution at 70±1 °C in the presence of benzoyl peroxide (BPO) as a free radical initiator. The terpolymers were characterised by 1H NMR, 13C NMR and FTIR spectroscopic techniques. The terpolymer compositions were determined using 1H NMR analysis. The polydispersities of the terpolymers with values between 1.66 and 1.85 suggest a strong tendency for chain termination by disproportionation. The glass transition temperatures of the terpolymers are found to be between those of the corresponding homopolymers and relative to their content. Increase in the nBA or THFA contents and decrease in the GMA content in terpolymers results in a decrease in the glass transition temperatures. The determination of MRR for the ternary system was obtained by employing the EVM model. Experimental terpolymerisation data agree well with calculations based on the Alfrey-Goldfinger equation and the unitary and binary azeotropes were calculated.