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Access to the β-scission rate coefficient in acrylate radical polymerization by careful scanning of pulse laser frequencies at elevated temperature

Abstract

A novel method to estimate the β-scission rate coefficient (kβ) in radical polymerization of acrylates is introduced, provided that the backbiting and tertiary propagation rate coefficient have already been determined at sufficiently low temperatures at which β-scission is negligible (<< 350 K). The method relies on the sensitivity of kβ upon a change of the pulse laser frequency (<< 200 Hz) under isothermal pulsed laser polymerization (PLP) conditions in the temperature range between ca. 350 and 415 K, leading to a sufficient variation of the times scales of the radicals involved. These observations are not significantly influenced by macropropagation and thermal self-initiation, as respectively confirmed by in silico testing and experimental data. Solution inflection point data (e.g. solvent butyl propionate) are needed at the lower temperature range (350-410 K), whereas bulk inflection point data suffice at the higher temperature range (410-415 K). The proposed method leads to an estimated kβ value of at 413 K with bulk PLP data, suggesting a high propensity of macromonomer formation in acrylate polymerization under high temperature radical polymerization conditions, exceeding the previously suggested levels (kβ = 6 x 100-1.45 x102 s 1).

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Publication details

The article was received on 14 Aug 2018, accepted on 13 Sep 2018 and first published on 14 Sep 2018


Article type: Paper
DOI: 10.1039/C8RE00171E
Citation: React. Chem. Eng., 2018, Accepted Manuscript
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    Access to the β-scission rate coefficient in acrylate radical polymerization by careful scanning of pulse laser frequencies at elevated temperature

    A. B. Vir, Y. Marien, P. Van Steenberge, C. Barner-Kowollik, M. Reyniers, G. B. Marin and D. D'hooge, React. Chem. Eng., 2018, Accepted Manuscript , DOI: 10.1039/C8RE00171E

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