Blending Ferulic Acid Derivatives and Polylactic Acid into Biobased and Transparent Elastomeric Materials with Shape Memory Properties

Abstract

Thanks to its remarkable properties such as sustainability, compostability, biocompatibility, and transparency, poly-Llactic acid (PLA) would be a suitable replacement for oil-based polymers should it not suffer from low flexibility and poor toughness, restricting its use to rigid plastic by excluding elastomeric applications. Indeed, there are few fully biobased and biodegradable transparent elastomers−PLA-based or not−currently available. In the last decades, many strategies have been investigated to soften PLA and enhance its toughness and elongation at break by using plasticizers, oligomers, or polymers. This work shows how a ferulic acid-derived biobased additive (BDF) blends with a common rigid and brittle commercial grade of polylactic acid to provide a transparent non-covalently cross-linked elastomeric material with shape memory behavior exhibiting an elongation at break of 434% (vs 6% for pristine PLA). Through a structure−activity relationship analysis conducted with BDF analogues and a modeling study, we propose a mechanism based on π−π stacking to account for the elastomeric properties. Blending ferulic acid derivatives with polylactic acid generates a new family of fully sustainable transparent elastomeric materials with functional properties such as shape memory.

Strategic Approach Towards Plastic Waste Valorization: Challenges and Promising Chemical Upcycling Possibilities

“…An interesting example of PLA utilization could be the synthesis of elastomeric material with shape memory properties by blending with ferulic acid-derived additive, thus creating high-value application opportunities. [162] Despite the term biodegradable, which is used for this polymer, it is worth mentioning that PLA is biodegradable under simulated composting conditions, where the temperature is generally around 58°C. [163] Biodegradation typically happens via chemical hydrolysis to form low-molecular-weight oligomers that further break down to minerals by the action of microorganisms.…”

Monomers and Macromolecular Materials from Renewable Resources: State of the Art and Perspectives

“…In a similar vein, ferulic acid was used as a platform to synthesize an AB-type polycondensation monomer, ferulic acid methyl ( E )-3-(4-(2-hydroxyethoxy)-3-methoxyphenyl)acrylate, which was then polymerized with dimethyl terephthalate or dimethyl succinate, respectively, and aliphatic diols [ 169 ]. Another interesting approach considered the incorporation of the ferulic acid-derived bis-O-dihydroferuloyl-1,4-butanediol into rigid and brittle commercial-grade polylactic acid (PLA), yielding a non-covalently crosslinked elastomeric material exhibiting an elongation at break of 434%, a value that is way higher than of pristine PLA [ 168 ].…”

“… ( a ) Ketalization of levulinic acid and pentaerythritol for the synthesis of a cyclic polycondensation monomer [ 168 ]. ( b ) Synthesis of a bio-based allyl ether monomer from vanillin [ 167 ].…”

Improved Processability and Antioxidant Behavior of Poly(3-hydroxybutyrate) in Presence of Ferulic Acid-Based Additives

“…Due to the various functional groups, it can be easily functionalized and its phenol group usually carry on antioxidant properties even after functionalization. Ferulic acid derivatives were recently found to have plasticizing effects on polylactic acid (PLA) and polycaprolactone (PCL) [35][36][37].…”