Reactive Extrusion of Active Packaging Materials
It is estimated that 30 – 40% of the global food supply is wasted each year, largely due to physiochemical degradation reactions leading to consumer rejection of the food product. Nonmigratory active packaging is an emerging technology that has the potential to extend the shelf life of food while also adhering to consumer “clean” label demands with fewer preservatives and additives. In this work, we characterize the interfacial behavior of the previously synthesized polylactic acid-graft-nitrilotriacetic acid (PLA-g-NTA) polymer films through the determination of the carboxylate pKa of the NTA moieties (3.97 & 8.99). Furthermore, the results of a pH dependent ABTS radical scavenging assay demonstrated the use of the NTA grafted films as an antioxidant active packaging material in pH’s above 6.74, thus emphasizing the importance of applications-based research to predict performance in complex food matrices. Next, a nonmigratory active packaging material was developed through a condensation reaction of the primary amines of branched polyethyleneimine (PEI) and the maleic anhydride moieties of polypropylene-graft-maleic anhydride blended with polypropylene (PP¬-g-MA). PEI is a polycation with reported chelation, antimicrobial, and antioxidant properties. The grafting was confirmed through ATR-FTIR spectroscopy, where the blue shift of the C=O stretching of the PP-g-MA from 1708 cm -1 to 1702 cm -1 post extrusion suggests the formation of the maleimide group in the treated sample. The nonmigratory status of the treated polymer was confirmed with a 10 - day migration assay in food relevant solvents with a maximum migration rate of 0.022 mg / cm 2 in 3% acetic, significantly below the EU threshold of 0.1 mg / cm 2. An AO7 amine density assay confirmed the introduction of 7.22 nmol / cm 2 surface oriented primary amines, while a TBO carboxylic acid density assay confirmed the disappearance of surface bound carboxylic acids of PP-g-MA after extrusion with PEI, suggesting a successful condensation reaction. ABTS and DPPH radical scavenging assays demonstrated the antioxidant active properties of the aminated films with values of 5.90 and 4.31 nmol / cm 2 Troloxeq, respectively, while a viscosity dependent ABTS assay confirmed the use of the treated films in viscosities as high as 812.9 cPs (Troloxeq - 2.98 nmol / cm 2). Aminated films were unable to prevent the degradation of ascorbic acid or inhibit bacterial growth of both gram-negative and gram-positive in any practical capacity, restricting its use as a metal chelating or antibacterial active food packaging. The bulk pKa of the primary amines (10.07, 9.66 – 11.42 95% CI), measured using a pH dependent AO7 assay, is likely the reason for the lack of chelation or antibacterial properties. Dynamic water contact angle results exhibited the increased hydrophobic nature of the treated films with advancing water contact angles of 134.8 ° ± 9.7 °, nearing the superhydrophobic classification of ≥150 °. There was no significant change to the water vapor permeability of the treated films compared to the polypropylene control, demonstrating their use in food applications to protect water sensitive products. Treated samples exhibited no significant change in young’s modulus, tensile strength, or elongation at break compared to PP-g-MA, allowing it to be easily processed in current polymer processing facilities. Overall, the presented work provides a translatable method of developing an aminated antioxidant nonmigratory active packaging material for use in target applications. Furthermore, the tools designed and utilized here (applications-based method development, reactive extrusion polymer modifications) may help to broaden the use of functional materials into biomedical devices, wastewater treatment, carbon capture, diagnostics, and more.