Spectroscopic Analyses on Chain Structure and Thermal Stabilization Behavior of Acrylonitrile/Methyl Acrylate/Itaconic Acid-based Copolymers Synthesized by Aqueous Suspension Polymerization

We have synthesized a series of copolymers with different compositions of acrylonitrile (AN, 80–100 wt%), methyl acrylate (MA, 4–20 wt%) and itaconic acid (IA, 0–3 wt%) by using an efficient aqueous suspension polymerization, and have investigated the molecular structure and thermal stabilization behavior of PAN homopolymer, AN/MA-based bipolymers, and AN/MA/IA-based terpolymers by adopting ¹H/¹³C-NMR and thermal FT-IR analyses. The viscosity-average molecular weight of the synthesized polymers were measured to be ~263,000 g/mol. The reactivity ratios of AN and MA for all the copolymers were evaluated to be 0.99 and 1.05, respectively. Accordingly, the output compositions of the synthesized copolymers were quite consistent with the input monomer compositions. The ¹³C NMR analysis revealed that all the synthesized polymers have an atactic chain configuration, regardless of the feed composition. The structural evolutions during the thermal stabilization process of the copolymers in air environment were characterized by monitoring the temperature-dependent changes of characteristic absorbance bands at 2240 cm^-1 (C≡N), 1595 cm^-1 (C=N) and 1660 cm^-1 (C=O) with aid of thermal FT-IR spectroscopy. It was found that the IA unit in the terpolymers accelerated the oxidation and cyclization reactions, unlike the retarding effect of MA unit, and that the onset temperatures of the oxidation reaction of the copolymers with IA unit was lower than that of the cyclization reaction.