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Investigations into the Mass Spectrometric Method for the Determination of the Mode of Termination in Radical Polymerization
Author(s) -
Alghamdi Majed M.,
Russell Gregory T.
Publication year - 2013
Publication title -
macromolecular chemistry and physics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.57
H-Index - 112
eISSN - 1521-3935
pISSN - 1022-1352
DOI - 10.1002/macp.201200734
Subject(s) - chemistry , chain transfer , radical polymerization , methyl methacrylate , solvent , polymerization , chain termination , disproportionation , polymer chemistry , polymer , organic chemistry , catalysis
Abstract The fraction of termination by disproportionation, λ , in radical polymerization may be determined by a mass spectrometric (MS) analysis of the resulting polymer. It is subjected to an array of stringent consistency checks, working with polymerizations of methyl methacrylate at 85 °C in three different solvents and with four different initiators. λ is shown to be unaffected by the choice of initiator, initiator concentration, or isoviscous solvent. These findings serve to allay any fears about the method being undermined by effects such as primary radical termination or chain transfer to solvent, thereby establishing its robustness. At the same time, direct evidence for the occurrence of chain transfer to the solvent methyl isobutyrate is uncovered, and the importance of knowing other rate‐parameter values accurately, if λ is to be determined accurately, is illustrated. By carrying out MS analyses, it is concluded that electrospray ionization with time‐of‐flight detection gives the best results for the present purpose.