TY - JOUR
T1 - Electron-Poor Butenolides
T2 - The Missing Link between Acrylates and Maleic Anhydride in Radical Polymerization
AU - Lepage, Mathieu L
AU - Alachouzos, Georgios
AU - Hermens, Johannes G H
AU - Elders, Niels
AU - van den Berg, Keimpe J
AU - Feringa, Ben L
PY - 2023/8/9
Y1 - 2023/8/9
N2 - Butenolides are a class of 5-membered lactones that hold great potential as bio-based monomers to replace oil-derived acrylates, of which they are cyclic analogues. Despite this structural resemblance, the reactivity of the unsaturated ester moiety of electron-poor butenolides leans toward that of maleic anhydride, another essential monomer that does not homopolymerize but copolymerizes in a highly alternating fashion with polarized electron-rich comonomers. By studying the reactivity of 5-methoxy and 5-acyloxy butenolides through a combination of kinetics and density functional theory (DFT) experiments, we explain why electron-poor butenolides constitute a missing link between acrylates and maleic anhydride in radical polymerization.
AB - Butenolides are a class of 5-membered lactones that hold great potential as bio-based monomers to replace oil-derived acrylates, of which they are cyclic analogues. Despite this structural resemblance, the reactivity of the unsaturated ester moiety of electron-poor butenolides leans toward that of maleic anhydride, another essential monomer that does not homopolymerize but copolymerizes in a highly alternating fashion with polarized electron-rich comonomers. By studying the reactivity of 5-methoxy and 5-acyloxy butenolides through a combination of kinetics and density functional theory (DFT) experiments, we explain why electron-poor butenolides constitute a missing link between acrylates and maleic anhydride in radical polymerization.
U2 - 10.1021/jacs.3c04314
DO - 10.1021/jacs.3c04314
M3 - Article
C2 - 37498188
SN - 0002-7863
VL - 145
SP - 17211
EP - 17219
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 31
ER -