The ring-opening polymerization (ROP) of l-lactide (l-LA) was induced by the catalytic action of bismuth subsalicylate (BiSS) using linear aliphatic diols [HO(CH2) n OH, where n = 2, 3, 4, 5, 6, and 8] as initiators and chain transfer agents. The theoretical and experimental degree of polymerization (DP) in all samples of α,ω-hydroxy telechelic poly(l-lactide) (HOPLLAOH) had a good agreement in all samples, an effect attributed to the interaction of BiSS with HO(CH2) n OH inducing a transfer reaction. HOPLLAOH was synthesized and characterized by a range of analytical techniques, confirming the insertion of methylene groups from the initiator into the main chain of the polyester. The glass-transition temperature (T g) of HOPLLAOH was found to be proportional to the number of methylene groups present in the diol. Various parameters regarding the ROP of l-LA were studied, such as temperature, time of reaction, amount of catalyst, and the nature of the diols. A kinetic study of the reaction allowed the determination of the rate constants (k) and activation energy (E a). A mechanism of initiation is proposed based on a computational study using density functional theory (DFT), evidencing the role of the alkyl diol as an initiator, producing an alkoxide (Bi-OROH). This species then acts as a nucleophile, attacking the carbonyl group, inducing its insertion, and ultimately completing the ring-opening of l-LA.
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