Bimetallic Catalytic Systems Based on Sb, Ge and Ti for the Synthesis of Poly(ethylene terephthalate-co-isosorbide terephthalate)

The insertion of rigid monomers such as isosorbide into poly(ethylene terephthalate) (PET) allows for the access of polymers with improved properties, notably in terms of thermal stability. This biobased monomer is however poorly reactive, and harsh reaction conditions lead to color concerns regarding the resulting polymer. This has motivated the development of catalytic systems enabling an increase of the reaction rate and a good coloration. In this study, we have assessed bimetallic catalytic systems based on the main metals used for PET catalysis, i.e., antimony, germanium and titanium, for the synthesis of poly(ethylene terephthalate-co-isosorbide terephthalate) (PEIT). The Sb₂O₃/Ti(OiPr)₄ combination leads to a high reaction rate while maintaining an acceptable coloration. On the other hand, combining Sb₂O₃ with GeO₂ affords the formation of poly(ethylene terephthalate-co-isosorbide terephthalate) without coloration concerns and a reaction rate higher than that observed using the single metal catalysts. Molecular weights and microstructure including diethyleneglycol (DEG) and isosorbide contents are also discussed, together with the thermal properties of the resulting PEIT. The GeO₂/Ti(OiPr)₄ is also assessed, and leads to average performances.