Abstract
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.
Highlights
Poly(ethylene terephthalate) (PET) is one of the major polymers produced worldwide
Sb2 O3, GeO2, Ti(OiPr)4 and their combinations were assessed as catalysts for the synthesis poly(ethylene terephthalate-co-isosorbide terephthalate)
Sb based catalysts lead to the highest isosorbide incorporation, an acceptable coloration but the lower reactivity
Summary
Poly(ethylene terephthalate) (PET) is one of the major polymers produced worldwide. Due to its good mechanical, thermal and barrier properties, this semi-crystalline thermoplastic is notably used for liquid packaging. Most ofMost the of catalytic systems currently and used the synthesis of poly(ethylene terephthalate) are based on three metals: antimony, germanium and titanium [11,12]. Synergistic effects were reported using a combination of antimony with a heterogeneous aluminum assessed for the synthesis of PEIT, leading to higher coloration of the final polymer than Sb and Ge based co-catalyst for the synthesis of poly(ethylene terephthalate-co-ethylene isophthalate) [20]. Synergistic effects were reported using a combination of antimony with a heterogeneous aluminum based co-catalyst for the synthesis of poly(ethylene terephthalate-co-ethylene isophthalate). Alternative strategies combining transesterification, cyclization and polycondensation and leading to isosorbide terephthalate based poly(ester-co-carbonate) copolymers were proposed in the literature [21]. We provide a comparison of the performances of the single metal catalysts in terms of kinetics, microstructure, molecular weights and color of the polymer obtained, which is lacking in the current literature as far as we know
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