Ring-Opening Polymerization of Lactides by (Pyrazol-1-ylmethyl)pyridine Zn(II) and Cu(II) Complexes: Kinetics, Mechanism and Tacticity Studies

Abstract

The kinetics, mechanism and polymer microstructure studies of ring-opening polymerization (ROP) of lactides (LA) by Zn(II) and Cu(II) complexes of (pyrazolylmethyl)pyridine ligands, 2-(3,5-dimethylpyrazol-1-ylmethyl)pyridine (L1) and 2-(3,5-diphenylpyrazol-1-ylmethyl)pyridine (L2) is described. The complexes [Zn(Ac)₂(L1)] (1), [Cu(Ac)₂(L1)] (2), [Zn(Ac)₂(L2)] (3) and [Cu₂(Ac)₄(L2)₂] (4) formactive initiators in the ROP of D,L-LA and L-LA monomers. Generally Zn(II) complexes 1 and 3 exhibit higher activities compared to the corresponding Cu(II) complexes 2 and 4. Polymerization kinetics of D,L-LA show higher rates compared to the L-LA reactions. All the polymerization reactions follow pseudo first-order kinetics with respect to monomer while 1 shows second-order dependency on the polymerization reactions. Molecular weights of the polymers range from 813 g mol^–1 to 9207 g mol^–1 and exhibit relatively narrow molecular weight distributions between 1.2 to 1.6. While poly(D,L-LA) are predominantly atactic, poly(L-LA) are largely isotactic. All polymerization reactions proceed through coordination insertion mechanism followed by hydrolysis of the end groups.

KEYWORDS Zinc and copper complexes, lactide, polymerization, kinetics, mechanism.

PDF and Supp files attached