Abstract
AbstractHeteroatom‐containing polymers have strong potential as sustainable replacements for petrochemicals, show controllable monomer–polymer equilibria and properties spanning plastics, elastomers, fibres, resins, foams, coatings, adhesives, and self‐assembled nanostructures. Their current and future applications span packaging, house‐hold goods, clothing, automotive components, electronics, optical materials, sensors, and medical products. An interesting route to these polymers is the catalysed ring‐opening copolymerisation (ROCOP) of heterocycles and heteroallenes. It is a living polymerization, occurs with high atom economy, and creates precise, new polymer structures inaccessible by traditional methods. In the last decade there has been a renaissance in research and increasing examples of commercial products made using ROCOP. It is better known in the production of polycarbonates and polyesters, but is also a powerful route to make N‐, S‐, and other heteroatom‐containing polymers, including polyamides, polycarbamates, and polythioesters. This Review presents an overview of the different catalysts, monomer combinations, and polymer classes that can be accessed by heterocycle/heteroallene ROCOP.
Highlights
Synthetic polymers are structurally tuneable materials integral to modern life whether for commodity products, like clothing, food packaging or house-hold goods, or for specialist applications, such as microelectronics, renewable energy generation or robotics.[1]
The success story of last centuries polymers has its origin in close coupling with the liquid fuel industry, optimized production methods, low costs and immense chemical diversity; these features allow for material properties to be precisely tailored to a huge range of different applications
In 2020, we reported a heterodinuclear Co(III)K catalyst, coordinated by an asymmetric diphenolate, diamine macrocycle featuring a tetra-ether moiety, that showed excellent activity in propene oxide (PO)/CO2 ring-opening copolymerisation (ROCOP) (TOF 800 h-1, 70 °C, 0.025 mol%, 30 bar CO2, 93% PPC).[62]
Summary
Synthetic polymers are structurally tuneable materials integral to modern life whether for commodity products, like clothing, food packaging or house-hold goods, or for specialist applications, such as microelectronics, renewable energy generation or robotics.[1]. The polycarbonates prepared by CO2/epoxide ROCOP are usually the kinetic reaction product which provides an opportunity to chemically recycle them to either cyclic carbonates or the parent monomers.[3] Lu and co-workers reported a di-Cr(III) catalyst for N-heterocyclic epoxide/CO2 ROCOP, showing >99% polymer selectivity at 60 °C.[63] at 100 °C the near quantitative depolymerisation occurred re-forming the epoxide and CO2.
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