Evolution of molecular weight distributions in the catalytic chain transfer polymerization of methyl methacrylate up to high monomer conversions

Christopher Kowollik, Thomas P. Davis

Research output: Contribution to journalArticleResearchpeer-review

19 Citations (Scopus)


The evolution of molecular weight distributions (MWDs) with monomer conversion in the catalytic chain transfer (CCT) polymerization of methyl methacrylate at 60°C is investigated by simulation (via the program package PREDICI) and experiment. A Co(III)-based complex is used as the precursor for the CCT agent, which is formed in situ by initiator-derived (2,2′-azobisisobutyronitrile) radicals to yield the catalytically active Co(II) species. The small shifts seen in the MWD toward lower molecular weights with increasing monomer conversion are shown to be of the same order of magnitude as the associated changes in the MWD in non-CCT controlled free-radical polymerization, indicating that no significant change in the MWD with monomer conversion is associated with the CCT process. These results are compared to the evolution of MWDs in conventional chain transfer polymerizations with thiols as transfer agents. A clear shift toward higher molecular weights is seen with increasing monomer conversion, indicating disparate rates of thiol and monomer consumption.

Original languageEnglish
Pages (from-to)3303-3312
Number of pages10
JournalJournal of Polymer Science, Part A: Polymer Chemistry
Issue number18
Publication statusPublished - 15 Sept 2000
Externally publishedYes

Cite this