Cyclopolymerization. XXI. Radical cyclopolymerization of n,n-diallylmethacrylamide

N,N-Diallylmethacrylamide (DAMA) was synthesized and its radical cyclopolymerizability was investigated. Polymerizations of DAMA were found to proceed according to the standard kinetic equation for radical polymerization except for the diffusion controlled termination reactions owing to higher viscosity of DAMA, in spite of the fact that it contains two allyl groups. DAMA yields polymers with slightly higher degree of cyclization than 50% in dilute solution polymerization. With increasing monomer concentration, the degree of cyclization decreases gradually and it becomes slightly lower value than 50% in concentrated solution polymerizations. It was found that about 86% of pendant unsaturations is allyl group and the rest is methacryloyl group. Structural studies on repeating units showed that possibility for the presence of bicyclic structures (those formed with consumption of three double bonds involved in DAMA) and structural units with two pendant unsaturations (those formed with one double bond in DAMA participated in polymerization) is extremely small. Main repeating cyclic unit was assigned to five-membered monocyclic lactam with an allyl group on its nitrogen, the content of which is estimated to be approximately 86% based on the allyl content. The main fraction of the rest of repeating cyclic structures was attributed to monocyclic pirolidine ring with a methacryloyl group on its nitrogen. These structural investigations and ESR studies of DAMA revealed that the methacryloyl group of DAMA is less reactive than its allyl group as in the case of N-methyl-N-allylmethacrylamide which has already been reported. © 1995 John Wiley & Sons, Inc.