The synthesis of a series of antioxidant polymers with varied capability to scavenge radicals and alter the wettability of surfaces is reported.

While antioxidants are widely known as natural components of healthy food and drinks or as additives to commercial polymer materials to prevent their degradation, recent years have seen increasing interest in enhancing the antioxidant functionality of newly developed polymer materials and coatings. This paper provides a critical overview and comparative analysis of multiple ways of integrating antioxidants within diverse polymer materials, including bulk films, electrospun fibers, and self-assembled coatings. Polyphenolic antioxidant moieties with varied molecular architecture are in the focus of this Review, because of their abundance, nontoxic nature, and potent antioxidant activity. Polymer materials with integrated polyphenolic functionality offer opportunities and challenges that span from the fundamentals to their applications. In addition to the traditional blending of antioxidants with polymer materials, developments in surface grafting and assembly via noncovalent interaction for controlling localization versus migration of antioxidant molecules are discussed. The versatile chemistry of polyphenolic antioxidants offers numerous possibilities for programmed inclusion of these molecules in polymer materials using not only van der Waals interactions or covalent tethering to polymers, but also via their hydrogen-bonding assembly with neutral molecules. An understanding and rational use of interactions of polyphenol moieties with surrounding molecules can enable precise control of concentration and retention versus delivery rate of antioxidants in polymer materials that are critical in food packaging, biomedical, and environmental applications.

We report on mechanically strong, water-insoluble hydrogen-bonded nanofiber mats composed of a hydrophilic polymer and a natural polyphenol that exhibit prolonged antioxidant activity. The high performance of fibrous mats resulted from the formation of a network of hydrogen bonds between a low-molecular-weight polyphenol (tannic acid, TA) and a water-soluble polymer (polyvinylpyrrolidone, PVP) and could be precisely controlled by the TA-to-PVP ratio. Dramatic enhancement (5- to 10-fold) in tensile strength, toughness, and Young’s moduli of the PVP/TA fiber mats (as compared to those of pristine PVP fibers) was achieved at the maximum density of hydrogen bonds, which occurred at ∼0.2–0.4 molar fractions of TA. The formation of hydrogen bonds was confirmed by an increase in the glass-transition temperature of the polymer after binding with TA. When exposed to water, the fibers exhibited composition- and pH-dependent stabilities, with the TA-enriched fibers fully preserving their integrity in acidic and neutral media. Importantly, the fiber mats exhibited strong antioxidant activity with dual (burst and prolonged) activity profiles, which could be controlled via fiber composition, a feature useful for controlling radical-scavenging rates in environmental and biological applications.

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We explore synthetic polymeric antioxidants as powerful inhibitors of corrosion of metals. Antioxidant copolymers were designed to have polyphenol, gallol, or catechol moieties along with hydrophobic groups brought by hexyl methacrylamide units. The polymers were deposited on aluminum alloy 2024-T3 as submicrometer thick films of individual polymers or as 10 wt % additives to epoxy-based ∼100 μm thick coatings. Thin antioxidant polymer films provided significant corrosion protection of AA2024. Unlike poly(hexyl methacrylamide), which lacked polyphenol functional units, the antioxidant polymers were compatible with standard epoxy coatings and provided exceptional protection of surfaces in extreme corrosion conditions (0.6 M NaCl solution) for over 100 days. Anticorrosion performance of antioxidant-containing coatings was characterized using scanning electron microscopy, optical microscopy, and electrochemical impedance spectroscopy (EIS) and further evaluated with the equivalent electrical circuit analysis of the EIS data. Importantly, unlike small-molecule analogues, such as tannic acid, antioxidant copolymers were not leachable from epoxy coatings into water or ethanol. Taken together, these results show that antioxidant copolymers are efficient materials for protection of metals against corrosion.