Thiocarbonyl chemistry in polymer science

Abstract

Organised by reaction type, this review highlights the unique reactivity of thiocarbonyl (C=S) groups with radicals, anions, nucleophiles, electrophiles, in pericyclic reactions, and in the presence of light. In the...

Lactide-derived monomers for radical thiocarbonyl addition ring-opening copolymerisation

“…4,7 A few years ago, the groups of Gutekunst 8 and Roth 9 independently reported the thionolactone dibenzo[c,e]-oxepane-5thione (DOT) as a means to produce degradable polythioesters by so-called thiocarbonyl addition ring-opening (TARO) polymerisation. In this process, growing radicals add to CvS bonds 10 followed by fragmentation and ring-opening to form a new propagating radical, by analogy with reversible additionfragmentation chain transfer (RAFT) polymerisation. 11 DOT monomer was shown to exclusively introduce ring-opened thioester backbone units in acrylate, 8,9 acrylamide, 9,12 and maleimide-based polymers.…”

Xanthate-supported photo-iniferter (XPI)-RAFT polymerization: facile and rapid access to complex macromolecules

“…This observation fits well with the difference in radical stabilization energy of an acrylate (resembling the R-group) and an acrylamide (resembling a macro-CTA that is reactivated). 47 As the radical formed by the acrylamide is less stabilized, a β-fragmentation would be less favourable from the macro-CTA, leading to an overall lower radical concentration. In this case the reaction would slow down once free Xan is consumed.…”

Addition–Fragmentation Ring‐Opening Polymerization of Bio‐Based Thiocarbonyl l‐Lactide for Dual Degradable Vinyl Copolymers

“…[16][17][18][19][20] More recently, the radical addition-fragmentation ring-opening of cyclic thiocarbonyl compounds was utilized for the radical copolymerization of thionolactone with vinyl monomers. A thionolactone monomer, dibenzo[c,e]oxepane-5thione, could be copolymerized with various vinyl monomers to afford copolymers with thioester linkages in the main chain after quantitative addition-fragmentation ring-opening, [21][22][23][24][25] and a caprolactone-derived thionolactone was also found to be amenable to radical polymerization, although the comonomer was limited to vinyl esters. [26,27] We aimed to develop a novel thiocarbonyl-containing comonomer derived from biorenewable resources and to copolymerize it with various vinyl monomers to afford degradable vinyl polymers.…”