Bis-Beta-(Diketonates) Zn(Ii) Complexes Substituted With Thiophene: Electropolymerization, Homogeneous And Heterogeneous Catalysis For Ring Opening Polymerization Of Lactide

ABSTRACT Two Bis‐β‐diketonate zinc (II) complexes were synthesized using 1‐(thiophen‐2‐yl)butane‐1,3‐dione and 1‐(thiophen‐2‐yl)‐3‐(thiophen‐3‐yl)propane‐1,3‐dione as ligands. By electropolymerization of their thiophenyl groups, the metallopolymers deposited on FTO electrodes were obtained. The main objective was to study the reactivity of these compounds as ROP catalysts for PLA synthesis, using directly the zinc complexes (homogeneous catalysis) and also the modified electrodes with metallopolymers (heterogeneous catalysis). The homogeneous catalysis studies allowed the optimization of the polymerization conditions, such as reaction time, catalyst concentration, and the use of benzyl alcohol as cocatalyst, as well as their influence on the conversion rate, average molecular weight and polydispersity of PLA, using rac ‐LA and L‐LA as monomers. Also, the effect on tacticity and thermal properties were discussed. Finally, the ROP studies using immersed modified electrodes in the polymerization medium were carried out under optimized experimental conditions. These tests were positive for one of the studied compounds, reaching conversions of up to 67%. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58 , 557–567