Exovinylene Cyclic Carbonates: Multifaceted CO₂‐Based Building Blocks for Modern Chemistry and Polymer Science

Abstract

Carbon dioxide is a renewable, inexhaustible, and cheap alternative to fossil resources for the production of fine chemicals and plastics. It can notably be converted into exovinylene cyclic carbonates, unique synthons gaining momentum for the preparation of an impressive range of important organic molecules and functional polymers, in reactions proceeding with 100 % atom economy under mild operating conditions in most cases. This Review summarizes the recent advances in their synthesis with particular attention on describing the catalysts needed for their preparation and discussing the unique reactivity of these CO2‐based heterocycles for the construction of diverse organic building blocks and (functional) polymers. We also discuss the challenges and the future perspectives in the field.

Biodegradable isocyanate-free polyurethane films via a noncatalytic route: facile modified polycaprolactone triol and biobased diamine as precursors

“…Despite the synthesis of polyurethanes pioneered by Bayer involving the polyaddition of a polyol with isocyanate, the recent approaches in this field have advanced towards the strategy of isocyanate-free routes to form isocyanate-free polyurethanes (PU). 1–4 In conventional PU, the reaction of polyols ( f n = 2 to 6) with isocyanate raised concerns due to their water sensitivity, hazards and health risk, which prompted us to select alternative precursors. 5–10 To protect the environment and to tackle the depletion of fossil feedstocks, non-degradable PU need to be replaced by isocyanate free and/or biodegradable PU that are similar to conventional PU in terms of their physicochemical and mechanical properties.…”

Catalyst-Free Approach for the Degradation of Bio- and CO2-Sourced Polycarbonates: A Step toward a Circular Plastic Economy

“…In the past years, our group pioneered the fabrication of a new class of (semicrystalline) polycarbonates (poly­(oxo-carbonate)) by the room-temperature polyaddition of CO 2 -sourced bis­(exovinylene cyclic carbonate)­s and diols, some of them having already shown promising utilization as solid electrolytes for Li-ion batteries. − Despite both monomers finding a CO 2 and biorenewable origin, the end-of-life recycling scenario of these polymers is unknown and has to be evaluated to meet the sustainability goals of our modern society. These polycarbonates structurally differ from their conventional analogues by the presence of additional ketone moieties within or pending along the main skeleton.…”

Unifying Step-Growth Polymerization and On-Demand Cascade Ring-Closure Depolymerization via Polymer Skeletal Editing

“…Herein, we report an original and facile methodology to fabricate polycarbonate-type polymers with cascade ring-closing depolymerization ability via an activated chain-end mechanism, delivering new cyclic scaffolds upon deconstruction. Capitalizing on our recent approach of furnishing regioregular polycarbonates by room-temperature step-growth copolymerization of exovinylene biscyclic carbonates and diols, − we envisioned that the smart skeletal editing of these PCs should solve the conflict between step-growth copolymerization and ring-closing depolymerization. Thus, we explore the introduction of additional unprotected in-chain secondary functionalities, which are nonreactive at room temperature but activated on demand upon catalytic thermal switching (Scheme ).…”