Cyclocopolymerization of Allyl-Acrylate Quaternary Ammonium Salts with Diallyldimethyhlammonium Chloride

摘要

A series of copolymers of N,N-dialkyl-N-2-(methoxycarbonyl)allyl allyl am- monium chloride, N,N-dialkyl-N-2-(ethoxycarbonyl)allyl allyl ammonium chloride, and N,N-dialkyl-N-2-(t-butoxycarbonyl)allyl allyl ammonium bromide with diallyldimeth- ylammonium chloride (DADMAC) were prepared in water at 60 °C with 2,2'-azo-bis(2- amidinopropane)dihydrochloride. A strong effect of ester substituents on cyclopolymer- ization was observed. The methyl and ethyl ester monomers showed high cyclization efficiencies during homopolymerizations and copolymerizations. Unexpectedly, the t- butyl ester derivatives sbowed high crosslinking tendencies. Water-soluble copolymers were obtained only with a decrease in the molar fraction of t-butyl ester monOmer below 30%. Relative reactivities of the allyl-acrylate monomers in photopolymerizations were compared with the relative reactivity ofDADMAC. AIlyl-acrylate monomers were much more reactive than DADMAC; the photopolymerization rate decreased in the following order: N,N-morpholine-N-2-(t-butoxycarbonyl)allyl allyl ammonium bromide > N,N- piperidyl-N-2-(t-butoxycarbonyl)allyl allyl ammonium bromide > N,N-dibutyl-N-2- (ethoxycarbonyl)allyl allyl ammonium chloride > N,N-piperidyl-N-2-(ethoxycarbony- l)allyl allyl ammonium chloride -N,N-morpholine-N-2-(ethoxycarbonyl)allyl allyl am- monium chloride -N;N-piperidyl-N-2-(methoxycarbonyl)allyl allyl ammonium chloride > N-methyl-N-butyl-N-2-(ethoxycarbonyl)allyl allyl ammonium chloride. Intrinsic viscos- ities of the polymers measured in 0.09 M NaCI ranged from 1.06 to 3.20 dUg. The highest viscosities were obtained for copolymers of the t-butyl ester 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.