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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

✍ Scribed by Michael Buback; Christopher Kowollik


Publisher
John Wiley and Sons
Year
1999
Tongue
English
Weight
93 KB
Volume
200
Category
Article
ISSN
1022-1352

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✦ Synopsis


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 l 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 8C 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.


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