Abstract
N-Substituted N-allyl-2-(methoxycarbonyl)allylamines (SAMC) were synthesized and polymerized to establish a methodology for designing unconjugated dienes with not only a high cyclization tendency but also high polymerizability. The N-substituents investigated were methyl, propyl, tert-butyl, and phenyl groups. Detailed examination of the properties of the unconjugated dienes reported so far indicated the use of functional groups with a higher conjugative nature together with no homopolymerization tendency to be essential to achieve this purpose. SAMC were designed since α-substituted acrylates have a considerably higher conjugative nature, even if they do not have homopolymerization tendencies. In fact, conjugation between C=C and C=O double bonds of the acryloyl groups of SAMC and N-substituted N-propyl-2-(methoxycarbonyl)-allylamines (SPMC), one of the monofunctional counterparts of SAMC, were found to be considerably effective. No detectable homopolymer could be obtained from SPMC. It is well known that allyl compounds, the other monofunctional counterparts of SAMC, have extremely lower polymerization tendencies. SAMC were converted to completely cyclized polymers by use of a radical initiator with a high polymerization rate, especially in the case of methyl and propyl derivatives. Their polymerizabilities were correlated with the conjugative nature of C=C and C=O double bonds of their acryloyl groups, except for the phenyl derivative. ESR studies on the methyl derivative suggested that its polymerization initiates through the acryloyl group.
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Liu, QQ., Kodaira, T., Urushisaki, M. et al. Cyclopolymerization XXIII. Design of Unconjugated Dienes with High Polymerizability Using Functional Groups with No Homopolymerization Tendency and Synthesis of Completely Cyclized Polymers Therefrom: Radical Polymerizations of N-Substituted N-Allyl-2-(methoxycarbonyl)allylamines. Polym J 28, 1000–1005 (1996). https://doi.org/10.1295/polymj.28.1000
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DOI: https://doi.org/10.1295/polymj.28.1000
