N- and C-diallyl monomers of new structural types in radical polymerization: theoretical study on the mechanism of reaction

The cyclization and competing reactions for growing radical chains based on N-and C-diallyl monomers of new structural types have been investigated with density functional theory with B3LYP/6-311G(d) computations. The study of these reactions of five diallyl monomers, N,N-diallyl-N′-acetylhydrazine (DAAH) (I), 1,1-diallyl-3-methyl-2-(4-nitrofurazan-3-yl)guanidine (AMNG) (II), tris(diethylamino)diallylaminophosphonium chloride (DAAP-Cl) (III), 2,2-diallyl-1,1,3,3-tetraethylguanidinium chloride (AGC) (IV), 2-[(diallyl)hydroxymethyl]pyrrolidine (AGMP) (V), was carried out. The probability of homopolymerization is the highest in C-diallyl monomers. In neutral N-diallyl monomers, the reaction of intramolecular hydrogen abstraction proceeds more easily, whereas in the case of guanidinium salt, the availability of a charged guanidinium fragment leads to high efficiency of cyclopolymerization. These results are in good agreement with experimental data on the polymerization of N- and C-diallyl monomers of new structural types.