Seeded Emulsion Polymerization of Butyl Acrylate Using a Redox Initiator System: Kinetics and Mechanism

Abstract

Seeded emulsion polymerization of n-butyl acrylate (n-BA) was initiated by a redox initiator system: cumene hydroperoxide/ferrous sulfate hexahydrate/ethylene-diaminetetraacetic acid monosodium salt/sodium formaldehyde sulfoxylate (CHP−Fe2+−EDTA−SFS). Final poly(n-butylacrylate) (PBA) particles with narrow size distribution were obtained. The kinetics and mechanism of seeded emulsion polymerization initiated by the redox initiator system were investigated. Special care was focused on effects of component concentration of the redox initiator system on the seeded emulsion polymerization kinetics. Particle growth and pH variation during the polymerization were also studied. It was found that the polymerization rate and the overall conversion increased with increasing CHP and SFS concentration. Interestingly, the optimal molar ratio of CHP/SFS was 1.10/3.81 rather than being equimolar in our work. In addition, an optimal molar ratio of EDTA to ferrous ions (2.19 × 10−5 mol/7.12 × 10−6 mol) was found. The polymerization rate increased first and then decreased with increases in ferrous ion concentration. The pH value in the system decreased as the polymerization proceeded. A limiting conversion phenomenon of conversion not being able to exceed 20% was found, and an explanation to the limiting conversion was proposed on the basis of the views of the practical cumulative formation constant log KMY and reaction rate comparison. When another activator solution (EDTA/FES/SFS (mol) 2.19 × 10−5/7.12 × 10−6/1.91 × 10−3) was added, the limiting conversion was removed and the final conversion reached 97%.