Chain-length-dependent termination in acrylate radical polymerization studied via pulsed-laser-initiated RAFT polymerization

Michael Buback, Pascal Hesse, Thomas Junkers, Thomas Theis, Philipp Vana

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The chain-length dependence of the termination rate coefficient, k t, in methyl acrylate (MA) and dodecyl acrylate (DA) radical polymerization has been determined via the single pulse pulsed-laser polymerization near-infrared reversible addition?fragmentation chain transfer (SP-PLP-NIR-RAFT) technique. Polymerization is induced by a laser SP and the resulting decay in monomer concentration, cM, is monitored via NIR spectroscopy with a time resolution of microseconds. A RAFT agent ensures the correlation of radical chain length and monomer-to-polymer conversion. The obtained rate coefficients for termination of two radicals of approximately the same chain length, i, are represented by power-law expressions, k t(i,i) α i. For both monomers, composite model behaviour of kt(i,i) showing two distinct chain length regimes is observed. The exponent ?s referring to short chain lengths is close to unity, whereas the exponent ?l, which characterizes the chain-length dependency of large radicals, is slightly above the theoretical value for coiled chain-end radicals. The crossover chain length, ic, which separates the two regions, decreases from MA (ic ≤ 30) to DA (ic ≤ 20). The results for MA and DA are consistent with earlier data reported for butyl acrylate. There appears to be a correlation of ? s and ic with chain flexibility.

Original languageEnglish
Pages (from-to)779-787
Number of pages9
JournalAustralian Journal of Chemistry
Issue number10
Publication statusPublished - 15 Oct 2007
Externally publishedYes

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