Controlled Polymerization Catalysis for the Synthesis of Degradable Amphiphilic Polycarbonates from CO 2
Year: 2026
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Synthetic water-soluble polymers are ubiquitous in solution-based applications, but their petroleum origin and nondegradable bonds create environmental concerns. Here, CO 2 - and glycerol-derived polycarbonates incorporating hydrophilic diglycerol motifs are prepared as a general-purpose water-soluble degradable polymer platform. A high-performance heterodinuclear [Co(III)/K(I)] catalyst enables controlled ring-opening copolymerization (ROCOP) of CO 2 with an acetal-protected epoxide, delivering well-defined polycarbonates with low dispersity ( D̵ < 1.2) and predictable molecular weights (≈2000–20,000 g mol –1 ). The catalysis is tolerant to protic initiators (chain transfer agents, CTAs), enabling control over both chain length and end-group chemistry. Deprotection of the acetals is quantitative and affords water-soluble polycarbonates incorporating hydrophilic diglycerol motifs. Using natural hydrophobic initiators yields amphiphilic polymers that self-assemble in water to form nanostructures of ≈7–11 nm with a critical micelle concentration of ≈30 mg L –1 . These polymers are stable at either neutral or acidic pH but depolymerize in alkaline solution to form nontoxic small molecules. Degradation proceeds by hydroxyl chain-end–initiated backbiting, i.e. by self-immolation, with pH- and end-cap-dependent kinetics, with complete degradation occurring over minutes to one month. Overall, this renewable polycarbonate chemistry, which is ∼23 wt % CO 2 -derived; ∼77 wt % glycerol-derived, combines precise polymerization catalysis, spontaneous aqueous self-assembly and controllable aqueous degradability which are important for next-generation surfactants.
DOI: 10.1021/jacs.5c20433
Institutions: University of Oxford, University of Sheffield
Language: English
Subfield: Biomaterials
Field: Materials Science
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Funders: Unilever, Wellcome Trust, National Institute for Health and Care Research, University of Oxford, Wallonie-Bruxelles International, Medical Research Council, Engineering and Physical Sciences Research Council, John Fell Fund, University of Oxford, Biomedical Research Council, NIHR Oxford Biomedical Research Centre, Health Data Research UK
Awards: The Sustainable Chemicals and Materials Manufacturing Hub SCHEMA, High-sensitivity multinuclear 600 MHz NMR for synthesis, catalysis and functional materials, Cleaner Futures (Next-Generation Sustainable Materials for Consumer Products)., Switchable Polymer Manufacturing Delivering Sustainable Products, G8757989928
OpenAlex ID: W7128733677