Synthesis and characterization of a novel unsaturated polyester based on poly(trimethylene terephthalate)

Unsaturated aromatic polyesters were obtained by glycolysis of poly(trimethylene terephthalate) with cis-2-buten-1,4-diol followed by a solid-state polymerization. The glycolysis was performed in a batch mode as well as through a continuous process in a twin screw extruder. The degradation and subsequent rebuilding of the polymer chain during the course of reaction was followed by means of inherent and melt viscosity measurements, and 1H NMR terminal group analysis of the intermediates and the final products. Structural investigations revealed that this new approach resulted in melt processible unsaturated polyesters with cross-linkable sites having similar characteristics to that of the virgin saturated polyester. Although the processing temperature for the different reaction steps was sufficiently high (180−260 °C), no thermally induced cross-linking of the incorporated unsaturated bonds could be evidenced indicating that the obtained products remained stable during the production stage. For comparison purposes, a commercial unsaturated polyester (Vestodur©) was included in the investigations. UV irradiation of thin polyester films did not result in cross-linked products but in cis-trans isomerization of the incorporated bisoxybutenyl unit.