Kinetics and Mechanistic Investigation of Hydrotalcite-Catalyzed Melt Synthesis of Poly(ethylene terephthalate)

✍ Scribed by Faissal-Ali El-Toufaili; Gunter Feix; Karl-Heinz Reichert

• Publisher: John Wiley and Sons
• Year: 2006
• Tongue: English
• Weight: 241 KB
• Volume: 291
• Category: Article
• ISSN: 1438-7492
• DOI: 10.1002/mame.200600123

✦ Synopsis

Abstract

Summary: Hydrotalcite‐catalyzed polycondensation of BHET was studied by thermogravimetry to elucidate the kinetics. The reaction was found to follow second‐order kinetics with respect to hydroxyl end groups. The overall activation energy of the polycondensation was found to decrease with increasing catalyst concentration before it leveled out to the value of 93 kJ · mol^−1^ at high catalyst concentration. This is a result of the uncatalyzed reaction that takes place parallel to the catalyzed one. The activation energy of the uncatalyzed path was found to be 156 kJ · mol^−1^. IR spectroscopy and XRD showed that the monomer intercalates between the layers of hydrotalcite at the beginning of the reaction enabling the complexation of oxygen‐containing functional groups with the hydroxide groups of the catalyst. Based on these findings a polycondensation mechanism is proposed. One end group of the monomer is activated in the form of alkoxide that counterbalances the positive charge of the hydrotalcite layer. This alkoxide group attacks an ester carbonyl group fixed close to it, generating a new ester bond and a glycoxide species. The role of hydrotalcite is to activate the reactants, rendering the attacking hydroxyl group more nucleophilic and the ester carbonyl group more electrophilic, and at the same time fixing the reactant together in a favorable geometry.

Intercalation of BHET in the gallery of HT layers in a twisted alkoxide form.

magnified imageIntercalation of BHET in the gallery of HT layers in a twisted alkoxide form.