A catalytic process to produce glycolide, the cyclic dimer of glycolic acid (GA), is proposed. Glycolide is the key building block of the biodegradable plastic polyglycolic acid. Instead of the current industrial twoâstep route, which involves the polycondensation of GA and a subsequent backbiting reaction, a new route based on the gasâphase transesterification of methyl glycolate (MGA) over a fixed catalyst bed is presented. With specific supported TiO2 catalysts, a high glycolide selectivity of 75â78â% can be achieved at the thermodynamicallyâlimited equilibrium conversion of MGA (54â% at 300â°C, 5.6â
vol% MGA, 1â
atm). The absence of solvent and the continuous nature of the process should allow for easy product separation and recycling of unconverted esters, while the few sideâproducts, i.âe. linear alkyl glycolate dimers and trimers seem recoverable via methanolysis. The reaction is compared to the cyclization of other αâhydroxy esters, such as methyl lactate to lactide, over the same catalysts, in terms of kinetics and thermodynamics. The absence of a methyl substitution on the αâcarbon seems to lead to faster cyclization kinetics of MGA when compared to methyl lactate or the doubleâsubstituted methylâ2âhydroxyâisobutyrate. Contrarily, glycolide production is less favored thermodynamically compared to lactide. The absence of glycolide decomposition at temperatures up to 300â°C however allows to increase equilibrium conversion by taking the endergonic reaction to higher temperatures.