Skip to Main content Skip to Navigation
Journal articles

Aromatic Xanthates and Dithiocarbamates for the Polymerization of Ethylene through Reversible Addition-Fragmentation Chain Transfer (RAFT)

Abstract : Aromatic xanthates and dithiocarbamates were used as chain-transfer agents (CTAs) in reversible addition-fragmentation chain transfer (RAFT) polymerizations of ethylene under rather mild conditions (≤ 80 °C, ≤ 200 bar). While detrimental side fragmentation of the intermediate radical leading to a loss of living chain-ends was observed in a previous study of alkyl xanthate CTAs, this mechanism was absent for the aromatic CTAs. The loss of living chain-ends was nevertheless detected for the aromatic xanthates via a different mechanism based on cross-termination. Narrow molar-mass distributions with dispersities between 1.2 and 1.3 were still obtained up to number average molar masses Mn of 1000 g mol-1. In contrast, the loss of chain-ends was minor for dithiocarbamates, yielding polyethylene up to Mn = 3000 g mol-1 with dispersities between 1.4 and 1.8. While all systems investigated showed significant rate retardation, the dithiocarbamates are indeed the first CTAs giving polyethylene with a high livingness via RAFT polymerization, which finally offers the possibility to readily synthesize various new polyethylene-based polymer architectures.
Document type :
Journal articles
Complete list of metadata

https://hal.archives-ouvertes.fr/hal-02316556
Contributor : Franck d'Agosto Connect in order to contact the contributor
Submitted on : Tuesday, November 24, 2020 - 4:54:43 PM
Last modification on : Thursday, June 17, 2021 - 9:54:02 AM
Long-term archiving on: : Thursday, February 25, 2021 - 8:50:33 PM

File

Wolpers Manuscript-RAFT_with_a...
Files produced by the author(s)

Identifiers

Collections

Citation

Arne Wolpers, Cédric Bergerbit, Bastian Ebeling, Franck d'Agosto, Vincent Monteil. Aromatic Xanthates and Dithiocarbamates for the Polymerization of Ethylene through Reversible Addition-Fragmentation Chain Transfer (RAFT). Angewandte Chemie International Edition, Wiley-VCH Verlag, 2019, 58 (40), pp.14295-14302. ⟨10.1002/anie.201905629⟩. ⟨hal-02316556⟩

Share

Metrics

Record views

74

Files downloads

71