Issue 21, 2022

Chain-length dependence of the propagation rate coefficient for methyl acrylate polymerization at 25 °C investigated by the PLP-SEC method

Abstract

When applying the pulsed laser polymerization–size exclusion chromatography (PLP-SEC) method to determine the propagation rate coefficient (kp) for bulk methyl acrylate at 25 °C, the characteristic ratio L1/L2 of chain lengths controlled by pulsing is found experimentally to be markedly higher than the expected value of 0.5. In addition, the kp values determined are dependent on the pulse repetition rate. These results are interpreted with a power-law representation of the chain length (L) dependence of the value of kp for long radicals according to kLp = k0pLβ, where k0p represents the maximum “virtual” propagation rate coefficient for monomeric radicals. New equations are derived to estimate the values of β and k0p from experimental molar mass distributions (MMDs), with the validity of the procedure checked in silico by simulations. A comparison of the calculated and experimental MMDs is used to correct chain lengths obtained by the PLP-SEC method, with β and k0p estimated to be 0.12 ± 0.01 and 28 000 ± 2000 L mol−1 s−1, respectively, for chain lengths within 350 ≤ L ≤ 1200.

Graphical abstract: Chain-length dependence of the propagation rate coefficient for methyl acrylate polymerization at 25 °C investigated by the PLP-SEC method

Supplementary files

Article information

Article type
Paper
Submitted
19 Feb 2022
Accepted
01 May 2022
First published
03 May 2022

Polym. Chem., 2022,13, 3053-3062

Chain-length dependence of the propagation rate coefficient for methyl acrylate polymerization at 25 °C investigated by the PLP-SEC method

A. N. Nikitin, E. Dušička, I. Lacík and R. A. Hutchinson, Polym. Chem., 2022, 13, 3053 DOI: 10.1039/D2PY00225F

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