TY - JOUR
T1 - Dependence of O2 Depletion on Transition Metal Catalyst in Radical Polymerization of Cross-Linking Alkene Resins
AU - den Besten, Hugo
AU - Zhang, Yanrong
AU - Eijsink, Linda E.
AU - Sardjan, Andy S.
AU - Volker, Anouk
AU - Browne, Wesley R.
N1 - Publisher Copyright:
© 2025 The Authors. Published by American Chemical Society.
PY - 2025/4/21
Y1 - 2025/4/21
N2 - Cobalt(II) carboxylates show broad reactivity with peroxides and O2 and are the industry standard catalyst for the activation of peroxide initiators for the radical polymerization of alkenes under ambient conditions. Curing alkene-based resins containing cross-linking units, i.e., monomers containing two or more alkene units, is important in forming hard protective coatings and materials. The activation of peroxide initiators produces the propagating chain end radicals needed for polymerization. Since polymerization progress depends on the rate of initiator activation and the concentration of propagating radicals, interception of radicals by O2 can inhibit curing. Cobalt(II) carboxylates are used due to their reactivity in the presence of oxygen, even in resin coatings. Alternative catalysts based on manganese and iron are desirable. Hence, the impact of O2 on their performance in resin curing is of interest. Here, we use NIR emission and time-resolved spectroscopy, employing the O2-sensitive probe [Ru(ph2phen)3]2+, to determine the concentration of dissolved [O2] in alkene resins during curing with three representative catalysts, Co(II)(2-ethylhexanoate)2, Fe(II)-bispidine, and Mn(II)(neodecanoate)2. The rate of depletion of O2 is highly dependent on the catalyst used, but in all cases, it is well before the onset of the autoacceleration of polymerization in cross-linking resins.
AB - Cobalt(II) carboxylates show broad reactivity with peroxides and O2 and are the industry standard catalyst for the activation of peroxide initiators for the radical polymerization of alkenes under ambient conditions. Curing alkene-based resins containing cross-linking units, i.e., monomers containing two or more alkene units, is important in forming hard protective coatings and materials. The activation of peroxide initiators produces the propagating chain end radicals needed for polymerization. Since polymerization progress depends on the rate of initiator activation and the concentration of propagating radicals, interception of radicals by O2 can inhibit curing. Cobalt(II) carboxylates are used due to their reactivity in the presence of oxygen, even in resin coatings. Alternative catalysts based on manganese and iron are desirable. Hence, the impact of O2 on their performance in resin curing is of interest. Here, we use NIR emission and time-resolved spectroscopy, employing the O2-sensitive probe [Ru(ph2phen)3]2+, to determine the concentration of dissolved [O2] in alkene resins during curing with three representative catalysts, Co(II)(2-ethylhexanoate)2, Fe(II)-bispidine, and Mn(II)(neodecanoate)2. The rate of depletion of O2 is highly dependent on the catalyst used, but in all cases, it is well before the onset of the autoacceleration of polymerization in cross-linking resins.
UR - http://www.scopus.com/inward/record.url?scp=105002022201&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.5c00760
DO - 10.1021/acs.inorgchem.5c00760
M3 - Article
AN - SCOPUS:105002022201
SN - 0020-1669
VL - 64
SP - 7716
EP - 7725
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 15
M1 - 5c00760
ER -