Abstract
Radical polymerizations of polystyrene macromonomers having a methacryloyl end group with Mns of 2900 and 9600 were investigated in the presence of inert polystyrene (PSt) of the same molecular weight. Under homogeneous conditions, the viscosity of polymerization media was fixed with variation in macromonomer concentration ([M]) by fixing the sum of the concentrations of the macromonomer and inert PSt. The presence of the inert PSt increased both the degree of polymerization (DP) of poly(macromonomer)s and polymerization rate (Rp). The observed kinetic order of Rp with respect to [M] decreased by the addition of inert PSt, but remained larger than unity. Termination rate constant (kt) decreased by the addition of inert PSt and increase of [M], while the propagation rate constant (kp) was not affected by inert PSt. kp did not show clear [M]-dependence, irrespective of the presence of inert PSt. These results are discussed in terms of the viscosity of polymerization media, initiator efficiency and specific multibranched structure about the propagating radical.
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Tsutsumi, K., Tsukahara, Y. & Okamoto, Y. Radical Polymerization Behavior of Polystyrene Macromonomers in the Presence of Inert Polystyrene. Polym J 26, 1318–1324 (1994). https://doi.org/10.1295/polymj.26.1318
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DOI: https://doi.org/10.1295/polymj.26.1318