Enzymatic miniemulsion polymerization of styrene with a polymerizable surfactant

Abstract

Enzymatic polymerization is a powerful tool for synthesizing useful polymeric materials. However, the preparation of polymer particles by enzymatic polymerization has been reported only rarely. We demonstrated herein the preparation of polystyrene particles by enzyme-mediated miniemulsion polymerization with a polymerizable surfactant, i.e., N,N-dimethyl-N-n-dodecyl-N-2-methacryloyloxyethylammonium bromide (C₁₂-DMAEMA), using a horseradish peroxidase (HRP)/H₂O₂/β-diketone system in water. Effects of various amounts of HRP, H₂O₂, and β-diketone on styrene conversion and particle size were investigated. The obtained polystyrene particles were characterized using DLS, GPC, and SEM measurements, and the polymerization kinetics was examined. Comparison of five β-diketones was also conducted: acetylacetone (ACAC), ethylacetoacetate (EAA), 1,3-cyclopentanedione (CP), tetronic acid (TA), and dibenzoylmethane (DM), for enzymatic miniemulsion polymerization.