Cyclopolymerization. Part XXVII. Cyclopolymerizability of an unconjugated diene with functional groups with no homopolymerization tendency: radical polymerization of N-methyl-N-methallyl-2-(methoxycarbonyl)allylamine and structure of the polymers derived therefrom

Radical cyclopolymerizations of N-methyl-N-methallyl-2-(methoxycarbonyl) (1 ) were studied to see the validity of the proposal made previously. It stat es that the use of functional groups with a higher conjugative nature toget her with no homopolymerization tendency is essential for the design of 1,6- dienes with not only a high cyclization tendency but also high polymerizabi lity. Monomer 1 was designed, since non-homopolymerizability of both the mo nofunctional counterparts of 1 could be assumed reasonably based on the rep orted polymerization behavior of compounds with similar structures. The alp ha-substituted acryloyl group of 1 was found to have high conjugative natur e and polymerizations of 1 proceeded rapidly to yield polymers with degree of cyclization of 97% even in its bulk polymerizations. The results thus ob tained were fundamentally in accordance with what had been expected from th e proposal. Structural studies showed that poly(1) consists almost exclusiv ely of six-membered rings as repeat cyclic units. Mechanism for intramolecu lar cyclization during the cyclopolymerization of 1 was discussed based on the structural characteristics of poly(1) along with those reported for the polymers obtained from diallyl monomers. (C) 2000 Elsevier Science Ltd. Al l rights reserved.