Copolymerizations of 2-vinyl-l,3-dioxane (la), 5.5-bis(hydroxymethyl)-2-vinyl-1,3-dioxane (lb), and 5,5-dimethyl-2-vinyl-l,3dioxane (lc) with acrylonitrile (AN) and a-chloroacrylonitrile (CPAN) in N,N-dimethylformamide (DMF) were investigated. For the AN (Ml)/la (MJ, AN(Ml)/lb (M,), and AN (M,)/lc (M,) pairs, the copolymerization parameters r l are $2, 3,7, and 3,9, respectively. For the CPAN (M,)/la (M2), CPAN (Ml)/lb (M2), and CPAN (Ml)/lc (M,) pairs, the r 1 values are 7,95, 7,80, and 8 9 , respectively. In all cases the r2 value is approximately zero. A clearly different influence of the monomer feed composition on the copolymerization rate is observed when the reaction takes place in the absence of solvent compared with that made in DMF. The explanation is related with the existence of associations between acrylonitrile or z-acrylonitrile and the vinyl-dioxane compound.