On the kinetics and mechanism of copolymerization of vinyl acetate and itaconic monomers

Abstract The introduction of anionic hydrophylic groups in the pendant chain of polyvinyl alcohol improves its surface and adhesive properties. For the purpose of synthesizing raw materials for preparation of modified polyvinyl alcohol with enhanced performance characteristics, the copolymerization of vinyl acetate with itaconic acid and diethyl itaconate at concentrations up to 9 mol % in methanol solution using azo‐bis‐isobutyronitrile and tert‐butylcyclohexylperoxydicarbonate as initiators has been studied. The experiments were performed using two different methods of addition of the itaconic monomer—single, at the beginning of the process, and continuous. It was established that the process rate decreases as the quantity of the second comonomer increases. The reaction order in terms of itaconic acid ( −2, 95) and reactivity ratios for both pairs vinyl acetate and itacinic acid (r1 = 0.053 and r2 = 31) and vinyl acetate and diethyl itaconate (r1 = 0.125 and r2 = 18) were determined. The products obtained were characterized by IR and NMR. It was confirmed that for the case of single addition at the beginning of the process a two‐phase system is formed while the continuous addition resulted in random group distribution.