Abstract
This article is the first comprehensive review on the study and use of vinyl ester monomers in reversible addition fragmentation chain transfer (RAFT) polymerization. It covers all the synthetic aspects associated with the definition of precision polymers comprising poly(vinyl ester) building blocks, such as the choice of RAFT agent and reaction conditions in order to progress from simple to complex macromolecular architectures. Although vinyl acetate was by far the most studied monomer of the range, many vinyl esters have been considered in order to tune various polymer properties, in particular, solubility in supercritical carbon dioxide (scCO2). A special emphasis is given to novel poly(vinyl alkylate)s with enhanced solubilities in scCO2, with applications as reactive stabilizers for dispersion polymerization and macromolecular surfactants for CO2 media. Other miscellaneous uses of poly(vinyl ester)s synthesized by RAFT, for instance as a means to produce poly(vinyl alcohol) with controlled characteristics for use in the biomedical area, are also covered.
Highlights
Poly(vinyl ester)s have a rich history in polymer research and industrial production [1]
A recent example is the solubility of poly(vinyl acetate) (PVAc) in supercritical carbon dioxide that can be enhanced via the copolymerization of vinyl acetate (VAc) with hindered [3,4,5,6] or fluorinated vinyl esters [7,8,9]
In the case of the O-tert-butyl xanthate, theoretical calculations have shown that scission of the O-tert-butyl bond to form a tert-butyl radical is competitive with scission of the S-PVAc bond [99]
Summary
Poly(vinyl ester)s have a rich history in polymer research and industrial production [1]. The nature of the vinyl ester monomer can influence the stereochemistry of chain propagation and the tacticity of the resulting polymer, only to a limited extent due to the sp nature of the radical center This can be achieved by playing on either steric hindrance or polar effects by using bulky [13,14,15] or polar [14,16] substituents. Use of specific solvents [17,18]— fluoroalcohols [16,19,20,21,22]—or addition of Lewis acids [23] constitute other options to induce higher syndiotacticities [19] For these reasons, vinyl esters represent a large palette of monomers for creating materials with tuneable properties such as Tg, Tm, solubility (i.e., in scCO2), alkaline resistance and tacticity. The use of RAFT-derived poly(vinyl ester)s as precursors to PVA, as CO2-philic polymers or surfactants, and in several other applications will be described
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