Abstract
In order to establish the composition equation for the bulk-copolymerization of p-chlorostyrene (monomer 1) and methyl acrylate (monomer 2) at 40°C, an extraordinarily large number of careful polymerization runs were carried out covering a wide range of feed composition. The samples were analyzed for composition by both potentiometric titration for chlorine and combustion analysis for carbon. The optimum set of terminal-model parameters evaluated by a least-squares curve-fitting procedure are r1=1.21 and r2=0.144, quite at variance with the literature values, but conform to the Q–e scheme. However, the chlorine and carbon sets of data consistently indicate failure of the terminal model to accurately represent this system. The penultimate model parameters r1=0.92, r1′=2.3, and r2 (=r2′)=0.18 represent the system almost perfectly. This indicates the presence of significant penultimate effects on type-1 radicals. The question as to the penultimate effects on type-2 radicals remains to be answered.
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Fukuda, T., Ma, YD. & Inagaki, H. Free-Radical Copolymerization I. Reactivity Ratios in Bulk-Copolymerization of p-Chlorostyrene and Methyl Acrylate. Polym J 14, 705–711 (1982). https://doi.org/10.1295/polymj.14.705
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DOI: https://doi.org/10.1295/polymj.14.705
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