Cyclocopolymerization of allyl-acrylate quaternary ammonium salts with diallyldimethylammonium chloride

A series of copolymers of N,N-dialkyl-N-2-( methoxycarbonyl)allyl allyl amm onium chloride, N,N-dialkyl-N-2-(ethoxycarbonyl)allyl allyl ammonium chlori de, and N,N-dialkyl-N-2-(t-butoxycarbonyl)allyl ammonium bromide with diall yldimethylammonium chloride (DADMAC) were prepared in water at 60 degreesC with 2,2'-azo-bis(2-amidinopropane)dihydrochloride. A strong effect of este r substituents on cyclopolymerization was observed. The methyl and ethyl es ter monomers showed high cyclization efficiencies during homopolymerization s and copolymerizations. Unexpectedly, the t-butyl ester derivatives showed high crosslinking tendencies. Water-soluble copolymers were obtained only with a decrease in the molar fraction oft-butyl ester monomer below 30%. Re lative reactivities of the allyl-acrylate monomers in photopolymerizations were compared with the relative reactivity of DADMAC. Allyl-acrylate monome rs were much more reactive than DADMAC; the photopolymerization rate decrea sed in the following order: N,N-morpholine-N-2-(t-butoxycarbonyl)allyl ally l ammonium bromide > N,N-piperidyl-N-2-(t-butoxycarbonyl)allyl allyl ammoni um bromide > N,N-dibutyl-N-2(ethoxycarbonyl)allyl allyl ammonium chloride > N,N-piperidyl-N-2-(ethoxycarbonyl)allyl allyl ammonium chloride similar to N,N-morpholine-N-2-(ethoxycarbonyl)allyl allyl ammonium chloride similar t o N,N-piperidyl-N-2-(methoxycarbonyl)allyl allyl ammonium chloride N-methyl -N-butyl-N-2-(ethoxycarbonyl)all allyl ammonium chloride. Intrinsic viscosi ties of the polymers measured in 0.09 M NaCl ranged from 1.06 to 3.20 dL/g. The highest viscosities were obtained for copolymers of the t-butyl eater monomers with piperidine and morpholine substituents. The copolymer of the t-butyl ester with piperidine substituent and DADMAC was hydrolyzed in acid to give a polymer with zwitterionic character. (C) 2001 John Wiley & Sons, Inc.