Cu(0)-mediated reversible-deactivation radical polymerization of n-butyl acrylate in suspension

Abstract

Cu(0)-mediated reversible-deactivation radical polymerization of n-butyl acrylate was performed in suspension without the use of an organic solvent. In all cases, a 5 v% organic phase (monomer, initiator, and ligand) was used with respect to 95 v% aqueous phase. Polyvinyl alcohol (PVA) as a suspension stabilizer has been shown to be able to control the polymerization for the degree of polymerizations of 222 and higher. The polymerization reaction showed linear first-order kinetics for a PVA concentration range of 1–10 wt%, leading to polymers with dispersities from 1.22 to 1.43. Conversions as high as 96% were obtained in 55 min. Scanning electron microscopy analysis of the suspensions confirmed the formation of micron-sized polymer particles dispersed in aqueous media, and that the size of the particles decreased with increasing PVA concentration. Rheometry measurements of the aqueous phase containing PVA before and after polymerization demonstrated the increase in the viscosity of the reaction mixture after polymerization. The difference between the viscosity of the PVA solution in water and the same solution after polymerization decreased as the PVA decreased, which indicates smaller particle sizes formed with increasing PVA content. All suspensions were stable over a period of three months storage at room temperature without any precipitation or sedimentation. The maximum copper species concentration in the reaction medium and water can be as low as 7 ppm. This Cu(0)-mediated reversible-deactivation radical polymerization in suspension has the potential for industrial use, especially for paint and adhesives.