Synthesis and Cyclopolymerization of Novel Allyl-Acrylate Quaternary Ammonium Salts

摘要

Novel allyl-acrylate quaternary ammonium satls were synthesized using two different methods. In the first (method 10, N,N-dimethyl-N-2-(ethoxycarbonyl) allyl allylammonium bromide and N,N-dimethyl-N-2-(tert-butoxycarbonyl) allyl allylammonium bromide were formed by reacting tertiary amines with allyl bromide. The second (method 2) involved reacting N,N-dialkyl-N-allylamine with either ethyl #alpha#-chloromethyl acrylate (ECMA) or tert-butyl #alpha#-bromomethyl acrylate (TBBMA). The monomers obtained with the method 2 were N,N-diethyl-N-2-(ethoxycarbonyl) allyl allyammonium chloride, N,N-diethyl-N-2-(tert-butoxycarbonyl) allyl allylammonium bromide, and N,N-piperidyl-N-2-(ethoxycarbonyl) allyl allylammonium chloride. Higher purity monomers were obtained with the method 2. Solution polymerizations with 2,2'-azo-bis(2-amidinopropane) dihydrochloride (V-50) in water at 60-70 deg C gave soluble cyclopolymers which showed polyelectrolyte behavior in pure water. Intrinisic viscosities measured in 0.09M NaCl ranged from 0.45 to 2.45 dL/g. ~1H- and ~13C-NMR spectra indicated high cyclization efficiencies. The ester groups of the tert-butyl polymer were hydrolyzed completely in acid to give a polymer with zwitterionic character.