title: Termination Mechanism of the Radical Polymerization of Acrylates.
abstract: The termination mechanism of the radical polymerization of acrylates, namely the selectivity of disproportionation (Disp) and combination (Comb) between polymer end radicals, is unambiguously determined by the reaction of polyacrylate end radicals generated from corresponding "living" organotellurium ω-end polymer. While textbooks describe the occurrence of Comb, the reaction at 25 °C exclusively gives the Disp products. Ab initio molecular dynamics suggests that the products form by two pathways: The direct disproportionation reaction and a novel stepwise process that involves the initial formation of the C-O coupling product followed by intramolecular rearrangement. The termination at high temperature and low radical concentration increases the contribution of back-biting reaction giving mid-chain radicals, and complex reaction pathways of the mid-chain radicals are clarified for the first time.
authors.affiliation: Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Yasuyuki
authors.initials: Y
authors.lastname: Nakamura
authors.affiliation: ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia.
authors.forename: Richmond
authors.initials: R
authors.lastname: Lee
authors.affiliation: ARC Centre of Excellence for Electromaterials Science, Research School of Chemistry, Australian National University, Canberra, ACT, 2601, Australia.
authors.forename: Michelle L
authors.initials: ML
authors.lastname: Coote
authors.affiliation: Institute for Chemical Research, Kyoto University, Gokasho, Uji, Kyoto, 611-0011, Japan.
authors.forename: Shigeru
authors.initials: S
authors.lastname: Yamago
mesh_terms: D000179:Acrylates / Q000737:chemistry*; D005609:Free Radicals / Q000737:chemistry; D056004:Molecular Dynamics Simulation; D058105:Polymerization; D011108:Polymers / Q000737:chemistry*; D013696:Temperature; D013816:Thermodynamics
chemical_list: D000179:Acrylates; D005609:Free Radicals; D011108:Polymers
keywords: acrylates; molecular dynamics; radical polymerization; radical reactions; termination reactions