RAFT/MADIX (co)polymerization of vinyl trifluoroacetate: a means to many ends

Polymer Chemistry Pub Date: 2013-10-01 DOI: 10.1039/C3PY01109G

Abstract

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< ? <1.23) for theoretical Mn 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.

Graphical abstract: RAFT/MADIX (co)polymerization of vinyl trifluoroacetate: a means to many ends
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