Skip to Main content Skip to Navigation
Journal articles

Peroxide-Free and Amine-Free Redox Free Radical Polymerization: Metal Acetylacetonates/Stable Carbonyl Compounds for Highly Efficient Synthesis of Composites

Abstract : New peroxide-free, amine-free, and phosphine-free redox free radical polymerization (RFRP) initiating systems comprising remarkably stable (i) metal acetylacetonates (Mn(acac)(3), Cu(acac)(2)) and (ii) carbonyl compounds bearing labile hydrogen in the alpha-position are presented for polymerization initiation under mild conditions (under air, at room temperature, nonpurified monomers). The systems proposed in this work are competitive or even outranked the well-known peroxide-based RFRP reference in several criteria: (i) toxicity, (ii) stability, (iii) surface curing, (iv) overall double-bond conversions, and (v) workability of the RFRP mixture (longer gel times are now possible). Radical initiating reactions are studied using many complementary experimental/theoretical techniques: optical pyrometry, thermal imaging, Raman confocal microscopy, electron spin resonance (ESR), ESR spin trapping (ESR-ST), high-resolution electrospray ionization mass spectrometry ( HR-ESI-MS), density functional theory (DFT), simulations of bond dissociation energies (BDE), reaction enthalpies, and DFT simulations of seven unknown ESR-ST adducts. A full consistent picture of the chemical mechanisms involved in these new redox systems is provided.
Document type :
Journal articles
Complete list of metadatas

https://hal-amu.archives-ouvertes.fr/hal-02091855
Contributor : Didier Gigmes <>
Submitted on : Saturday, April 6, 2019 - 5:15:47 PM
Last modification on : Thursday, July 9, 2020 - 1:12:03 PM

Identifiers

Collections

Citation

Patxi Garra, Frédéric Dumur, Malek Nechab, Fabrice Morlet-Savary, Céline Dietlin, et al.. Peroxide-Free and Amine-Free Redox Free Radical Polymerization: Metal Acetylacetonates/Stable Carbonyl Compounds for Highly Efficient Synthesis of Composites. Macromolecules, American Chemical Society, 2018, 51 (16), pp.6395--6404. ⟨10.1021/acs.macromol.8b01360⟩. ⟨hal-02091855⟩

Share

Metrics

Record views

71