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1.3.2.3 Basic Research on Batch Lactide Synthesis and the Catalysts Used

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Noda and Okuyama reported on the batch synthesis of lactide from DP 15 prepolymer with various catalysts at 4–5 mbar and 190–245°C [74]. In a batch synthesis with 50 g of oligomer in a stirred flask, the evolution rate of crude lactide is rather constant and then starts to decline and the conversion levels off at 80–90%. The tin catalyst performed best compared with other catalysts and showed the lowest levels of racemization. Tin octoate (stannous 2‐ethylhexanoate) is a liquid catalyst that can be handled easily, is food grade, and is widely available.

Thinking in terms of mechanisms, the equilibrium concentration of lactide in an oligomer mixture is 5% or less, and it will boil off at low vacuum [6, 68]. The catalyst increases the rate of lactide formation by facilitating lactide formation by backbiting from hydroxyl chain ends of oligomers [4, 74]. In a batch experiment, the rate is initially constant, but during synthesis esterification also occurs, and the DP of the polyester rises concomitantly. The melt viscosity of the reaction mixture increases accordingly and at the end of a batch process, mixing the highly viscous residue becomes very difficult, which limits the extent to which the residue can be depleted of lactide.

In engineering terms, this means that mass transfer of lactide from the liquid to the gas phase decreases as viscosity increases. The balance between lactide production and lactide removal plays a role in all experiments that one might want to investigate on lab scale. For example, catalyst concentrations of 0.05–0.2 wt% tin(II) octoate are mentioned in the literature, but traditional experiments to verify the order of the reaction for the catalyst are difficult because of the influence of mass transfer limitations.

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