Syntheses of new amino‐functionalized methacrylates and their use in free radical polymerizations

For use in emulsion and solution copolymerization a series of novel amino‐functional methacrylates has been synthesized, most of which have seldom, or never, been described in the literature before. In this investigation, the preparation of the hydrochloric and/or tosylate salt of the monomers aminoethyl, 3‐amino‐1‐propyl, 5‐amino‐1‐pentyl, 6‐amino‐1‐hexyl and 11‐amino‐1‐undecyl methacrylate will be described, along with the characterization of the parameters water solubility, pK_a and chemical stability. The homopolymers of these monomers have been prepared and characterized. Results show the occurrence of an acyl migration upon neutralization of the monomers aminoethyl‐ and 3‐amino‐1‐propyl methacrylate. This migration does not occur in the monomer 5‐amino‐1‐pentyl methacrylate, which makes it possible to synthesize the neutralized monomer although, after neutralization, a Michael addition occurs, resulting in a limited lifetime. Copolymerizations have been performed in emulsion. The monomer aminopentyl methacrylate especially proved to be suitable for emulsion copolymerizations when used under controlled conditions. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1401–1415, 2001