We investigated the structure–property relationships between poly(vinyl acetate)-based (co)polymers and their solubility in supercritical carbon dioxide. Building on RAFT/MADIX polymerization, key macromolecular characteristics—chain length, chain-end group and composition—of these (co)polymers were studied. Their solubility in sc-CO₂ was determined by high-pressure infrared spectroscopy, thereby providing guidelines for their design.

In this study, RAFT/MADIX (co)polymerization of vinyl trifluoroacetate (VTFAc) is presented and the specific properties of the resulting polymers are discussed. Xanthate-mediated polymerization of VTFAc exhibits the features of a reversible-deactivation radical polymerization. The xanthate is responsible for a decrease in the overall rate of polymerization compared to conventional radical polymerization. In spite of a limited kinetic chain length mainly attributed to chain transfer to solvent, number-average molar masses increase with monomer conversion and dispersities remain very low (1.07< Đ <1.23) for theoretical M_n lower than 1.5 × 10⁴ g mol⁻¹. The obtained polymers are semi-crystalline with high melting points. The statistical copolymerization of vinyl acetate with VTFAc yields controlled polyvinyl esters with tunable thermal properties and tacticity. Well-defined PVAc-PVOH diblock copolymers are readily produced by selective methanolysis of the VTFAc units of the starting PVAc-PVTFAc diblock copolymer. The added value of VTFAc in the design of polyvinyl esters with enhanced CO₂-philicity is also explored through its copolymerization with vinyl pivalate. VTFAc is seen as a new multifaceted partner in the chemistry of controlled poly(vinyl esters) that can be used to finely tune polymer dispersity, tacticity, thermal properties, chemical stability and solubility in supercritical carbon dioxide.