Polymeric Antioxidant via ROMP of Bioderived Tricyclic Oxanorbornene Based on Vanillin and Furfurylamine

Abstract

Herein, a bioderived antioxidant oxanorbornene lactam monomer bearing a vanillyl moiety has been successfully synthesized. The monomer was synthesized via reductive amination of two biobased molecules, vanillin and furfurylamine, followed by tandem Diels−Alder and lactamization reactions with maleic anhydride. For comparison, an inactive monomer was prepared using benzaldehyde instead of vanillin. Rapid controlled polymerization of the tricyclic strained monomers has been conducted using ring opening metathesis polymerization. The resultant polymers were fully characterized, and their antioxidant potentials had been assessed. The monomer with the vanillyl moiety and its corresponding polymer showed exceptional antioxidant activities compared to the reference analogue with a benzyl pendant group. Indeed, the developed antioxidant polymer shows promising potential in the sustainable polymer industry for a smaller ecological footprint.

Vanillin-Based Polymers via Ring-Opening Metathesis Polymerization

“…To the best of our knowledge, only one report discusses ROMP of vanillin derivatives, but this work involves multiple synthetic steps for ROMP and does not investigate the possibility of copolymerization. 39 This limitation has prompted us to explore the potential of ROMP by synthesizing a scalable ROMP monomer from vanillin and applying copolymerization. We herein report the efficient transformation of biobased vanillin into homopolymers and triblock copolymers through ROMP for applications in UV-blocking films and highperformance TPEs (Figure 1).…”

“…However, there has been limited research on the application of ROMP to vanillin derivatives. To the best of our knowledge, only one report discusses ROMP of vanillin derivatives, but this work involves multiple synthetic steps for ROMP and does not investigate the possibility of copolymerization . This limitation has prompted us to explore the potential of ROMP by synthesizing a scalable ROMP monomer from vanillin and applying copolymerization.…”

Biobased, Degradable, and Conjugated Poly(Azomethine)s

“…The majority of reported biobased compounds for degradable electronics center on directly using the small molecule or readily available derivatives. − Compared to their small molecule counterparts, polymers offer extended conjugation lengths, a variety of molecular architectures, tunable morphologies, and tailored degradation sites. More recently, compounds such as indigo, − vanillin, − and eumelanin, , amongst others, − have been incorporated into electron-conducting polymers due to their commercial availability and inherent presence in nature. , For example, indigo has been used as an acceptor unit to create donor–acceptor semiconducting polymers , and divanillin has been copolymerized with aromatic diamines to create poly(azomethine)s. Carotenoids, which resemble polyacetylene, are of notable interest due to their documented high single-molecule conductance, , photoinduced charge transfer, − and known degradation pathways. − To our knowledge, the best example of a synthesized carotenoid with extended conjugation contained 27 alkene bonds . Given the rich diversity of carotenoid molecules, we can synthetically access a multitude of degradable conjugated polymers.…”

Antioxidative Behavior of an Eco-Friendly Chitosan-Based Biomass Macromolecular Antioxidant for Styrene–Butadiene Rubber (SBR)/Silica Composites

“…Rubber products are widely applied in many fields because of their outstanding high elasticity, such as tires, medical gloves, pipes, wires and cables, adhesives, etc. 1,2 However, due to the presence of plenty of unsaturated double bonds in the rubber matrix, the rubber molecule chains are prone to crosslinking or breaking induced by light or thermal oxygen, or ozone during processing and application, resulting in the deterioration of their performance and appearance, consequently shortening the lifetime of rubber products. 3,4 Generally, the addition of antioxidants during rubber compounding can delay the aging process of rubber materials and extend their service life.…”