Incorporation of isosorbide into poly(butylene terephthalate) via solid-state polymerization

The biomass-based monomer isosorbide was incorporated into poly(butylene terephthalate) (PBT) by solid-state polymerization (SSP) using the macrodiol monomer BTITB-(OH)2, which consists of isosorbide (I), terephthalic acid (T), and 1,4-butandiol (B) residues. This macromonomer can be synthesized by a simple one-pot, two-step reaction. Polymers with number-average molecular weights up to 100 000 g·mol-1 were readily synthesized from various ratios of PBT/BTITB-(OH)2. Their molecular weights, thermal properties, and colors were compared with corresponding copolyesters that were obtained by melt polycondensation. We found that Tm, Tc and especially Tg were superior for materials that were obtained by SSP. This is ascribed to differences in the microstructures of both types of copolyesters; the SSP products exhibit a more blocky structure than do the more random melt- polymerized counterparts. The SSP method resulted in much higher molecular weights and much less colored polymers, and it seems to be the preferred route for incorporating biobased monomers that exhibit limited thermal stability into engineering plastics. © 2008 American Chemical Societ