Synthesis, Kinetics and Mechanism of Terpolymerization of Styrene, Vinyl Acetate with Acrylonitrile Initiated by P-Nitrobenzyl Triphenyl Phosphonium Ylide
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Abstract
Synthesis of terpolymers consisting of two electron-donating monomers, viz. styrene and vinyl acetate with one electron-accepting monomer, <i>i.e.</i> acrylonitrile, initiated by p-nitrobenzyl triphenyl phosphonim ylide in dioxane as diluent at 65°C for 150 min has been studied. The kinetic expression is <i>R<sub>p</sub>α</i>[I]<sup>0.8</sup>[Sty] <sup>1.2</sup>[VA] <sup>1.4</sup> [AN]<sup>1.2</sup>. The terpolymer composition was determined by the Kelen-Tüdos method. The values of reactivity ratios using <i>r</i><sub>1</sub> (Sty + VA) = 0.1 and <i>r</i><sub>2</sub> (AN) = 0.005. The overall activation energy is 46 kJ●mol●L<sup>–1</sup>. The formation of terpolymer is confirmed by the FTIR spectra showing bands at 3030 cm<sup>–1</sup>, 1598 cm<sup>–1</sup>, and 2362 cm<sup>–1</sup>, confirming the presence of phenyl, acetoxy and nitrile group respectively. The terpolymer has been characterized by <sup>1</sup>H-Nuclear Magnetic Resonance, <sup>13</sup>C-Nuclear Magnetic Resonance. The Differential Scanning Calorimetric curve shows the <i>T<sub>g</sub></i> of the polymer as 149.5°C. A scanning electron microscope confirms the polymer to be phosphorus free. Electron.Spin.Resonance spectra confirms phenyl radical responsible for initiation.
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