Solvent Effect on the Radical Copolymerization of N-Methyl- and N,N-Dimethylacrylamides and N-Methylmethacrylamide with Methyl Methacrylate

Abstract

ABSTRACT:Solvent effect on radical copolymerizations of N-methylacrylamide (AA) and Nmethylmethacrylamide (MA) with methyl methacrylate (MMA, M2) was studied using benzene (BZ), dioxane (DO), acetonitrile (ACN), ethanol (EtOH), and N,N-dimethylformamide (DMF). Spectroscopic studies revealed that the solvents influence these amide monomers (M1) with regards to their association by hydrogen-bonding and dipole-dipole interaction. The solvent ability which makes the self-associations of AA and MA more effective decreases in the order of BZ >DO> ACN > EtOH > DMF. The higher the solvent ability for the self-associations of the amide monomers, the larger the values of r1. The extent of the solvent effect on both the monomers decreased with decreasing order of their self-association tendencies, i.e., AA> MA. M 1 concentration around M 1 • radical is considered to be enhanced by its association with M 1 in the solvent with higher ability for the self-association of M1. This enhances the propagation-rate between M 1 • radical and M 1 and increases apparently k11 as compared with k 12 . The r 2 values did not change depending on solvents except the copolymerization in BZ. The interactions between MMA and the amide monomers are too weak to raise their local concentrations around M2 • radical. BZ iii.creases extraordinarily r1 and decreases r2 , respectively. Copolymers precipitated during copolymerization in BZ are considered to adsorb the amide monomers, since their interactions with BZ are extremely weak. This increases the local M1 concentration around both M1 • and M2 • radicals. BZ influences even the copolymerization of N,N-dimethylacrylamide which has been considered to be independent of the solvents. Dipole-dipole interaction has been ascribed to this solvent effect.KEY WORDS Solvent Effect / Radical Copolymerization / NMR / IR /

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