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Termination kinetics in free‐radical bulk terpolymerization — the systems methyl acrylate – butyl acrylate – dodecyl acrylate and methyl methacrylate – butyl methacrylate – dodecyl methacrylate
Author(s) -
Buback Michael,
Kowollik Christopher
Publication year - 1999
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/(sici)1521-3935(19990701)200:7<1764::aid-macp1764>3.0.co;2-f
Subject(s) - monomer , polymer chemistry , methyl methacrylate , chemistry , acrylate , methacrylate , methyl acrylate , butyl acrylate , photochemistry , polymer , organic chemistry
Termination rate coefficients, k t , for the terpolymerization of mixtures containing the three acrylates: methyl, butyl, and dodecyl acrylate or the corresponding members of the methacrylate family: methyl, butyl, and dodecyl methacrylate, have been measured via the single pulse (SP)‐PLP technique. In the homopolymerization of each of the six monomers an initial plateau region of almost constant k t is seen which extends at least up to 15% and, for dodecyl acrylate and dodecyl methacrylate, even up to about 50% monomer conversion. Terpolymerization k t in this region of low and moderate conversion is remarkably well described by a rather simple correlation which exclusively contains homopolymerization k t and the composition of the monomer mixture. This correlation turns out to be very useful for the modeling of k t in mixtures of monomers that exhibit such an initial plateau region of k t . For the systems under investigation, terpolymerization k t may be estimated within ± 30%. This finding is very remarkable in view of the enormous differences in homopolymerization k t within each monomer family, e. g., k t of methyl acrylate exceeds the corresponding dodecyl acrylate value by a factor of 50 (or 5 000%). The entire set of experiments has been carried out at 40°C and 1 000 bar where the signal to noise ratio of the laser‐induced single pulse experiments is very satisfactory. No reason is seen why the conclusions about modeling of terpolymerization k t should not be valid at other reaction conditions including ambient pressure.