A systematic study of tert‐butylacrylamide‐methyl acrylate‐acrylic acid radical solution terpolymerization

Abstract Multi‐functional polymers used for personal care products can be synthesized by radical polymerization of acrylic acid (AA) in alcohol/water solutions with non‐functional monomers such as methyl acrylate (MA) and N ‐ tert ‐butylacrylamide ( t ‐BuAAm). However, solvents capable of forming or disrupting hydrogen bonds cause the polymerization kinetics of these monomers to deviate from their polymerization behaviour in bulk and non‐polar solvents. In this work, a previous mechanistic model developed for MA/ t ‐BuAAm copolymerization is extended to represent the terpolymerization system MA/ t ‐BuAAm/AA. The additional kinetic coefficients required for the system are estimated from fitting to AA homopolymerizations and AA/MA and AA/ t ‐BuAAm copolymerizations conducted in an ethanol/water solution. In‐situ nuclear magnetic resonance (NMR) spectroscopy is used to follow monomer conversions and composition drift behaviour, with the molar mass distributions of the polymer products characterized by size‐exclusion chromatography. Although AA is more reactive than MA in non‐polar solvents, the reactivities of the two monomers equalize under the experimental conditions examined. Thus, the batch and semi‐batch terpolymerization data collected are represented equally well by a reduced acrylate/ t ‐BuAAm copolymerization model and the full terpolymerization implementation.