Abstract
The reaction of [ZnCl2] with N-cyclopentyl-1-(quinolin-2-yl)methanimine (LA), N-cyclohexyl-1-(quinolin-2-yl)methanimine (LB), N-cyclohexyl-1-(pyridin-2-yl)methanimine (LC), 2,6-diethyl-N-(pyridin-2-ylmethylene)aniline (LD), N-cyclopentyl-1-(pyridin-2-yl)methanimine (LE), and N-phenyl-(pyridin-2-yl)methanimine (LF) in ethanol produced the bidentate [(NN′)ZnCl2] complexes, [LAZnCl2], [LBZnCl2], [LCZnCl2], [LDZnCl2], [LEZnCl2] and [LFZnCl2], respectively. The molecular structures revealed that the zinc in [LnZnCl2] (Ln = LA − LD) showed a distorted tetrahedral geometry involving two nitrogens of N,N’-bidentate ligands and two chloride ligands. Most of these initiators were effective for polymerization of methyl methacrylate (MMA) and polymerization of rac-lactide (rac-LA). [LCZnCl2] (with N-cyclohexyl substituted at imine-pyridine moiety) exhibited the highest catalytic activity for MMA polymerization in the presence of modified methylaluminoxane (MMAO) with an activity of 3.33 × 104 g PMMA/mol·Zn·h at 60 °C, giving moderate syndiotactic poly methyl methacrylate (PMMA) with high molecular weight (9.62 × 105 g/mol). The dimethyl derivatives [LnZnMe2] (Ln = LA − LF), generated in situ, polymerized rac-LA with moderate activity and yielded a polylactide (PLA) with good number-average molecular weights and narrower polydispersity indices (PDIs). [LAZnMe2] effectively initiates the ring-opening polymerization (ROP) of rac-LA to attain heterotactic PLA (Pr = 0.91).
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