Understanding the Kinetics of the Atom Transfer Radical Polymerization of Vinyl Acetate in Bulk and Solution in Supercritical Carbon Dioxide
Year: 2025
Type: article
Abstract: High Resolution Image Download MS PowerPoint Slide Polymerizations in supercritical carbon dioxide (scCO 2 ) offer an ecofriendly and efficient method for polymer synthesis and processing. Most radical polymerizations carried out in scCO 2 will initially proceed as homogeneous polymerization until in situ generated high molar mass macromolecules phase separate. However, when the monomer concentration, acting as a cosolvent, is sufficiently high, macromolecular solubility is enhanced, allowing the reaction to proceed as a single-phase system even at high monomer conversion levels. This study analyzes previously reported kinetic data on the bulk atom transfer radical polymerization (ATRP) of vinyl acetate/ethyl-2-bromoisobutyrate/CuBr/2,2′:6′,2′-terpyridine at 70 °C and 1 bar, as well as solution ATRP in CO 2 at 60–70 °C and 310 bar. The perturbed-chain statistical associating fluid theory equation of state is used to estimate the solubility of the macromolecules in the reaction mixture in the case of ATRP in scCO 2 . The model predicts that poly(vinyl acetate) remains completely soluble in CO 2 throughout the reaction and the number-average chain-length increases linearly with monomer conversion for all nine case studies considered.
Language: English
Subfield: Biomedical Engineering
Field: Engineering
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G101085245, G514275850, G930406379
OpenAlex ID: W4415986932