Interpretation of the chain structures of PMMAs, PANs and PAAms obtained by using Ce(IV) and KMnO4 in combination with NTA and DTPA as initiator systems by FTIR spectroscopic analysis

Polyacrylamides (PAAms), polyacrylonitriles (PANs) and poly(methyl methacrylate)s (PMMAs) were synthesized by using Ce(NH₄)₂(NO₃)₆, Ce(SO₄)₂·4H₂O and KMnO₄ in combination with nitrilotriacetic acid (NTA) and diethylenetriamine pentaacetic acid (DTPA), which have strong chelating properties, as redox initiators. Polymerizations were carried out in the aqueous acidic solutions at 25°C and 55°C in the presence of air. The chain structures of the resulting products were studied by Fourier-transform infrared (FTIR) spectroscopic measurements. From the comparison of the spectroscopic results with gravimetric and viscometric data it was concluded that both the differences between the solubility behaviour in aqueous solutions of MMA, AN, AAm and their polymers, and catalyst–activator–monomer combinations were important parameters effecting the polymerization mechanisms, conversions and the structures of the polymers. The FTIR and viscosity results indicated that PAAms obtained in our experimental conditions formed crosslinked structures with sulphated complexes of Ce(III) and MnSO₄ produced by the redox reactions between catalysts (MnO₄⁻ and Ce(IV)), NTA and AAm. Further, it was observed that PAN chains were terminated by hydrated and sulphated complexes of Ce(III) while the termination of PMMA radicals took place by primary radicals because PMMAs were formed by emulsion polymerization kinetics.