Terpolymerization of maleic anhydride, trans-stilbene and acrylic monomers

The results of radical terpolymerization of maleic anhydride (MA), trans-stilbene (Stb) and acrylic monomers (n-butyl methacrylate (BMA) and acrylonitrile (AN)) as acceptor-donor-acceptor monomer systems are discussed. The structure and composition of terpolymers are determined by chemical (acid number for MA units) and elemental (content of N for AN units and O for BMA units) analyses, as well as by FTIR spectroscopy through recorded analytical absorption bands for MA (1770 and 1845 cm^-1), Stb (864 cm^-1) and BMA (1730 cm^-1) units, respectively. The considerable change in the terpolymer compositions is observed when a strong acceptor MA is substituted with BMA (or AN), having comparatively low acceptor character in the system studied. Copolymerization constants for the MA···Stb complex and acrylic comonomers pairs are determined according to the modified Kelen-Tüdös equation. Obtained results show that at the chosen ratios of comonomers, radical terpolymerization proceeded mainly by a true "complex" mechanism in the stage of near binary copolymerization of MA···Stb complexed monomers with free BMA (or AN). The kinetics of terpolymerization and terpolymer compositions are studied in the low and high conversion stages. It is shown that for the MA-Stb-BMA system the dependence of R_p on the concentration of individual comonomers has extreme character, while for BMA-Stb-AN this dependence does not have similar character. This fact indicated that terpolymerization in the BMA-Stb-AN system proceeds according to a classical statistical copolymerization mechanism. The terpolymer composition-thermal behaviour relationships are also studied by differential scanning calorimetry and thermogravimetric analysis methods.