Monomer Reactivity Ratios for the Copolymerization of Styrene with Pure Meta-and Pure Para-Divinylbenzenes

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Abstract
Reactivity ratios for the copolymerization of styrene (r 1) meta-divinylben-zene (r 2–m) and with para-divinylbenzene (r 2–p) have been redetermined under different reaction conditions and with different radioactivity assay techniques. The copolymers were prepared at two conversion levels [0.55 to 3.7% and 2.7 to 7.5% and at 80° (rather than 100°)] with benzoyl peroxide (in place of τ-butylhydroperoxide) initiator. The ionization chamber-vibrating reed electrometer radioactivity assay technique developed for other copolymerization studies was used in place of the direct counting technique previously used for the styrene/divinylbenzene systems. The new values are r 1 = 0.605/r 2-m = 0.88: r 1 = 0.77/r 2-p = 2.08 at 0.55 to 3.7% conversion and r 1 = 1.27; r 2–m = 1.08 at 2.7 to 7.5% conversion. These are not in close agreement with previous values partly because of the difference in conditions of copolymerization (temperature, per cent conversion, initiator) and in the improved analytical precision. Also the high-DVB-content (80%) para copolymer data are not assumed to be invalid and are not omitted (as they were before) from selection of the r 2–p values.

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