Novel Random Copolymers of Poly(butylene 1,4-cyclohexane dicarboxylate) with Outstanding Barrier Properties for Green and Sustainable Packaging: Content and Length of Aliphatic Side Chains as Efficient Tools to Tailor the Material's Final Performance.

The present paper describes the synthesis of novel bio-based poly(butylene 1,4-cyclohexane dicarboxylate)-containing random copolymers for sustainable and flexible packaging applications. On one side, the linear butylene moiety has been substituted by glycol subunits with alkyl pendant groups of different length. On the other side, copolymers with different cis/trans isomer ratio of cyclohexane rings have been synthesized. The prepared samples were subjected to molecular, thermal, diffractometric, and mechanical characterization. The barrier performances to O₂, CO₂, and N₂ gases were also evaluated. The presence of side alkyl groups did not alter the thermal stability, whereas it significantly influences the formation of ordered phases that deeply affect the functional properties, mainly in terms of mechanical response and barrier performance. In particular, the final materials present higher flexibility and significantly improved barrier properties with respect to the homopolymer and most polymers widely employed for flexible packaging. The improvement due to copolymerization was more pronounced in the case of higher co-unit-containing copolymers and for the samples with cyclohexane rings in the trans conformation.