Polymerisation of styrene using pincer type amine functionalized azo aromatic complexes of Co(ii) as catalysts

Abstract

In the present report, three mononuclear azo-aromatic complexes of Co(II), 1–3, and an imine-based Co(II) complex, 4, were synthesized through a reaction of respective amine-functionalized pincer-like ligands, HL^1–4, with CoCl₂·6H₂O in the ligand-to-metal ratio of 1 : 1. All the complexes, 1–4, were thoroughly characterized using various physicochemical characterization techniques, single-crystal X-ray structure determination, and density functional theory (DFT) calculations. Complexes 1–4 were explored for the catalytic styrene polymerisation reaction separately in the presence of modified methyl aluminoxane (MMAO). All the complexes, 1–4, are indeed active for the polymerisation of styrene under mild conditions at room temperature upon activation with MMAO. Among the azo-aromatic complexes 1–3, complex 3 is the most efficient. The activity of the imine complex 4 is poor compared to those of the azo-aromatic complexes 1–3. The weight average molecular weight (M_w) of the isolated polystyrene ranges from 32.9 to 144.0 kg mol⁻¹, with a polydispersity index (Đ) in the range of 1.1–1.8. Microstructural analysis of the isolated polymer from complexes 1–4 was carried out by ¹³C NMR spectroscopy, infrared spectroscopy, and powder X-ray diffraction studies. Their thermal properties were scrutinized by differential scanning calorimetry and thermogravimetric analysis. These studies have shown the atactic and amorphous nature of the polymers. The mechanical strength of the polymers was measured by a nanoindentation technique which has shown the good plastic/soft nature of the polymers.