Abstract
Cyclopolymerization of N-methyl-N-allyl-2-(t-butoxycarbonyl)allylamine (1a) and N-methyl-N-methallyl-2-(t-butoxycarbonyl)allylamine (1b) were undertaken to see the effect of a bulky ester t-butyl group on the cyclopolymerizabilities of N-substituted N-(meth)allyl-2-(alkoxycarbonyl)allylamines by comparing with those of N-methyl-N-(meth)allyl-2-(methoxycarbonyl)allylamine (2) and N-t-butyl-N-(meth)allyl-2-(methoxycarbonyl)allylamine (3). Non-homopolymerizability of the monofunctional counterparts of α-substituted acryloyl groups of 1a and 1b was confirmed. Polymerizability of 1a was almost similar to that of 2 with an N-allyl group and 1b polymerized faster than 2 with an N-methallyl group despite the fact that conjugative nature of the α-substituted acryloyl groups of 1 are less effective as compared with those of 2. The results were interpreted by assuming that steric effect of the bulky substituent influences more strongly on retarding termination rates than propagation rates of these monomers. Degrees of cyclization of poly(1a) and poly(1b) were found to be 100% and 96%, respectively. This indicates that the bulky ester t-butyl group influences the cyclopolymerizabilities of these 1,6-dienes in essentially different manner from those of the bulky N-substituent and we can design 1,6-dienes with both high cyclization and polymerization tendencies by introducing bulky group into proper position of these molecules. Repeat cyclic units of poly(1a) and poly(1b) were assigned to five- and six-membered rings, respectively.
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Kodaira, T., Satoyama, M., Urushisaki, M. et al. Cyclopolymerization XXIX. Radical Polymerizations of N-Methyl-N-(meth)allyl-2-(t-butoxycarbonyl)allylamines: Effect of a Bulky Ester Group on Cyclopolymerizability of 1,6-Dienes with Functional Groups of No Homopolymerization Tendencies. Polym J 32, 954–960 (2000). https://doi.org/10.1295/polymj.32.954
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DOI: https://doi.org/10.1295/polymj.32.954