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.
Polyesters constitute around 10% of the global plastic market with aromatic polyesters, such as poly(ethylene terephthalate) (PET), being the most prevalent because of their attractive properties. As for most commercial plastics, polyesters are primarily derived from fossil resources and are not readily degradable, which raises a number of sustainability concerns. Designing polymers with competitive properties from sustainable feedstocks that rapidly degrade under mild conditions is an attractive strategy for addressing the current plastic waste problem. Here, the detailed synthesis and characterization of degradable, high molar mass aromatic polyesters derived from salicylic acid, poly(salicylic glycolide) (PSG), and poly(salicylic methyl glycolide) (PSMG) are described. The synthesis of polymers was investigated through mechanistic experiments and complementary computational studies. The glass transition temperature (T g ≈ 85 °C) and Young's modulus (E ≈ 2.3 GPa) of these polyesters are comparable to those of PET. In contrast to the poor hydrolytic degradability of PET, both PSG and PSMG are readily degradable in neutral aqueous solutions (e.g., complete degradation in seawater at 50 °C in 60 days). These aromatic polyesters derived from salicylic acid have potential as future high-performance, sustainable, and degradable plastics.
N-heterocyclic carbenes (NHCs) belong to the popular family of organocatalysts used in a wide range of reactions, including that for the synthesis of complex natural products and biologically active compounds....
The control of the tacticity of synthetic polymers enables the realization of emergent physical properties from readily available starting materials. While stereodefined polymers derived from nonpolar vinyl monomers can be efficiently prepared using early transition metal catalysts, general methods for the stereoselective polymerization of polar vinyl monomers remain underdeveloped. We recently demonstrated asymmetric ion pairing catalysis as an effective approach to achieve stereoselective cationic polymerization of vinyl ethers. Herein, we provide a deeper understanding of stereoselective ion-pairing polymerization through comprehensive experimental and computational studies. These findings demonstrate the importance of ligand deceleration effects for the identification of reaction conditions that enhance stereoselectivity, which was supported by computational studies that identified the solution-state catalyst structure. An evaluation of monomer substrates with systematic variations in steric parameters and functional group identities established key structure−reactivity relationships for stereoselective homo-and copolymerization. Expansion of the monomer scope to include enantioenriched vinyl ethers enabled the preparation of an isotactic poly(vinyl ether) with the highest stereoselectivity (95.1% ± 0.1 meso diads) reported to date, which occurred when monomer and catalyst stereochemistry were fully matched under a triple diastereocontrol model. The more complete understanding of stereoselective cationic polymerization reported herein offers a foundation for the design of improved catalytic systems and for the translation of isotactic poly(vinyl ether)s to applied areas.
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