Propagation Rate Coefficient for Radical Polymerization of N-Vinyl Pyrrolidone in Aqueous Solution Obtained by PLP−SEC

Propagation rate coefficients, kp, of N-vinyl pyrrolidone (NVP) radical polymerization in aqueous solution have been measured via the pulsed-laser polymerization - size exclusion chromatography method (PLP−SEC) over an extended concentration range from 1.8 to 100 wt % NVP at temperatures between 2 and 60 °C. The SEC analyses have been carried out by a modified procedure using dimethyl acetamide as the eluent. An about 20-fold increase of kp is observed in passing from NVP bulk polymerization to reaction in dilute aqueous solution. As with nonionized methacrylic acid (MAA), for which a similarly strong change in kp has recently been reported, the large solvent effect in NVP polymerization is assigned to intermolecular interactions resulting in a significant hindrance of internal rotational motion in the transition state structure for propagation. Some contribution from a minor change in activation energy may however not be ruled out. PLP−SEC studies carried out on aqueous NVP solutions to which either poly...

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