Issue 34, 2017

A comprehensive kinetic study of the conventional free-radical polymerization of seven-membered cyclic ketene acetals

Abstract

The current study reports on the kinetic analysis of the free-radical polymerization of several seven-membered cyclic ketene acetal monomers and in particular 2-methylene-1,3-dioxepane (MDO) and 5,6-benzo-2-methylene-1,3-dioxepane (BMDO). Such monomers are known to undergo a complete ring-opening to afford polyester chains by a radical pathway. The influence of experimental conditions (e.g., nature and concentration of the initiator, temperature, solvent, etc.) on the kinetics and molar mass distribution was studied. Whereas it was shown that BMDO cannot be polymerized using peroxides due to H-abstraction, the experimental results also demonstrated that the polymerization kinetics were strongly driven by the nature of the propagating radical, with reactivity order: MDO > BMDO > 4,7-dimethyl-5,6-benzo-2(chloromethyl)-1,3-dioxepane (MeBMDO). The copolymerization of MDO and BMDO (1 : 1) was also investigated. The incorporation of both monomers was identical but the polymerization kinetics were governed by the monomer with the lowest reactivity. The experimental results were finally rationalized by the combination of DFT calculations of the propagation rate constants with PREDICI modelings.

Graphical abstract: A comprehensive kinetic study of the conventional free-radical polymerization of seven-membered cyclic ketene acetals

Supplementary files

Article information

Article type
Paper
Submitted
28 Cʼhwe. 2017
Accepted
29 Meur. 2017
First published
30 Meur. 2017

Polym. Chem., 2017,8, 5139-5147

A comprehensive kinetic study of the conventional free-radical polymerization of seven-membered cyclic ketene acetals

A. Tardy, J. Honoré, D. Siri, J. Nicolas, D. Gigmes, C. Lefay and Y. Guillaneuf, Polym. Chem., 2017, 8, 5139 DOI: 10.1039/C7PY00337D

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