Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research.

Transforming how plastics are made, unmade, and remade through innovative research and diverse partnerships that together foster environmental stewardship is critically important to a sustainable future. Designing, preparing, and implementing polymers derived from renewable resources for a wide range of advanced applications that promote future economic development, energy efficiency, and environmental sustainability are all central to these efforts. In this Chemical Reviews contribution, we take a comprehensive, integrated approach to summarize important and impactful contributions to this broad research arena. The Review highlights signature accomplishments across a broad research portfolio and is organized into four wide-ranging research themes that address the topic in a comprehensive manner: Feedstocks, Polymerization Processes and Techniques, Intended Use, and End of Use. We emphasize those successes that benefitted from collaborative engagements across disciplinary lines.

Diverse Proton-Conducting Nanotubes via a Tandem Macrocyclization and Assembly Strategy.

Macrocycles that assemble into nanotubes exhibit emergent properties stemming from their low dimensionality, structural regularity, and distinct interior environments. We report a versatile strategy to synthesize diverse nanotube structures in a single, efficient reaction by using a conserved building block bearing a pyridine ring. Imine condensation of a 2,4,6-triphenylpyridine-based diamine with various aromatic dialdehydes yields chemically distinct pentagonal [5 + 5], hexagonal [3 + 3], and diamond-shaped [2 + 2] macrocycles depending on the substitution pattern of the aromatic dialdehyde monomer. Atomic force microscopy and in solvo X-ray diffraction demonstrate that protonation of the macrocycles under the mild conditions used for their synthesis drives assembly into high-aspect ratio nanotubes. Each of the pyridine-containing nanotube assemblies exhibited measurable proton conductivity by electrochemical impedance spectroscopy, with values as high as 10-3 S m-1 (90% R.H., 25 °C) that we attribute to differences in their internal pore sizes. This synthetic strategy represents a general method to access robust nanotube assemblies from a universal pyridine-containing monomer, which will enable systematic investigations of their emergent properties.

Incorporating Functionalized Cellulose to Increase the Toughness of Covalent Adaptable Networks.

Covalent adaptable networks (CANs) are cross-linked polymers that have mechanical properties similar to thermosets at operating conditions yet can be reprocessed by cross-link exchange reactions that are activated by a stimulus. Although CAN exchange dynamics have been studied for many polymer compositions, the tensile properties of these demonstration systems are often inferior compared to those of commercial thermosets. In this study, we explore toughening CANs capable of forming covalent bonds with a reactive filler to characterize the trade-off between improved toughness and longer reprocessing times. Polycarbonate (PC) and polyurethane (PU) CANs were toughened by incorporating cellulose modified with cyclic carbonate groups as a reactive filler with loadings from 1.3 to 6.6 wt %. The addition of 6.6 wt % of the cellulose derivative resulted in a 3.2-fold increase in average toughness for the PC CANs, yet it only increased the characteristic relaxation time of stress relaxation (τ*) via disulfide exchange at 180 °C from 63 to 365 s. The cellulose-containing samples also showed >80% recovery in crosslinking density and mechanical properties after reprocessing. The addition of 3.2 wt % of the functionalized cellulose into a polyethylene glycol-based PU CAN led to a 2.3-fold increase in toughness while increasing τ* at 140 °C from 106 to 157 s. These findings demonstrate the promise of functionalized cellulose as an inexpensive, renewable, and sustainable filler that toughens CANs containing hydroxyl groups.

Synthesis of Multifunctional Homopolymers through Using Thiazolidine Chemistry and Post-Polymerization Modification.

Multifunctional homopolymers, defined here as polymers that contain multiple reactive functional groups per repeat unit, are versatile scaffolds for preparing complex macromolecules via post-polymerization modification. However, there are limited methods for preparing multifunctional homopolymers that contain more than one nucleophilic site per repeat unit. Herein, a strategy to synthesize a multifunctional homopolymer using thiazolidine chemistry is demonstrated. Controlled radical polymerization of a thiazolidine-containing acrylamido monomer allows for the synthesis of a polymer with pendent latent nucleophiles. Ring-opening of the thiazolidine affords a homopolymer with two side-chain reactive sites, an amine and a thiol. One-pot functionalization via disulfide formation and acyl substitution is performed to introduce two distinct groups in each repeat unit.