β‐Pinene‐Derived Polyesteramides and Their Blends: Advances in Their Upscaling, Processing, and Characterization

Abstract Terpene‐based polyesteramides (PEAs) are sustainable and have a variety of favorable properties, making them suitable for a wide range of applications and for contribution to a much more sustainable polymer industry. This work focuses on the synthesis of the lactam from β ‐pinene and its copolymerization with ε ‐caprolactone. An important step in synthesizing β ‐pinene lactam is the oxidation of β ‐pinene to nopinone. To make the established oxidative cleavage more sustainable and efficient, the required amounts of Al 2 O 3 and KMnO 4 are significantly reduced by using H 2 SO 4 as a catalyst. For the Beckmann rearrangement various catalysts and co‐reagents are screened. Among these, the reaction with tosyl chloride is found the most favorable. Subsequently, the chain lengths of the β ‐pinene‐based PEAs are remarkably increased from 6000 g mol −1 to more than 25 100 g mol −1 by fine‐tuning reaction time, temperature, and decreasing catalyst and initiator concentrations. Also, different catalysts for polymerization are tested. The resulting material shows melting temperatures of ≈55 °C and decomposition temperatures of 354 °C or higher. Processing via melt pressing or casting turned out to be quite difficult due to the polymer's brittleness. Furthermore, regarding biomedical applications, blends of PEA with polyethylene glycol were successfully prepared, yielding a more hydrophilic material.