Mechanistic investigations of antimony-catalyzed polycondensation in the synthesis of poly(ethylene terephthalate)

The chemical aspects of poly(ethylene terephthalate) synthesis via the antimony‐catalyzed polycondensation of hydroxy ethylene terephthalate end groups were studied to elucidate its mechanism. A polycondensation mechanism was proposed in which activation occurs by the formation of a chelate ligand on antimony composed of the hydroxyl end group and alcoholic oxygen of the ester of the same end group. The rate‐determining step of the polycondensation reaction was concluded to be the coordination of a second chain end to antimony. The low activity of antimony at a high concentration of hydroxyl end groups was proposed to result from the competition between hydroxyl end groups and the chelate structure leading to the transition state. The high selectivity of antimony is probably due to its relatively low Lewis acidity. Moreover, antimony was found to stabilize hydroxyl end groups against degradation by preventing their complexation to carbonyl functionalities. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1049‐1059, 2006 Antimony‐catalyzed synthesis of polyethylene terephthalate was studied to elucidate its mechanism. A polycondensation mechanism was proposed, in which activation occurs by formation of a chelate ligand on antimony composed of hydroxyl‐ and ester alcoholic oxygens of the hydroxy ethylene ester end groups. Polycondensation rate determining step was concluded to be coordination of a second chain end to antimony. Low activity of antimony at high concentration of hydroxyl end groups was proposed to result from competition between these groups and the chelate structure leading to the transition state. Antimony was found to stabilize hydroxy ethylene ester end groups against degradation.