Peroxide-Free and Amine-Free Redox Free Radical Polymerization: Metal Acetylacetonates/Stable Carbonyl Compounds for Highly Efficient Synthesis of Composites - Aix-Marseille Université Access content directly
Journal Articles Macromolecules Year : 2018

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.
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hal-02091855 , version 1 (06-04-2019)

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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, 2018, 51 (16), pp.6395--6404. ⟨10.1021/acs.macromol.8b01360⟩. ⟨hal-02091855⟩
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