Abstract: | Aqueous sulfonic acids (HOSO2R; R = CH3, Ph‐p‐CH3, and Ph‐p‐NO2), coupled with a water‐tolerant Lewis acid, ytterbium triflate Yb(OTf)3; OTf = ? OSO2CF3], initiate the cationic suspension polymerization of p‐methoxystyrene (pMOS) in heterogeneous aqueous media. They induce controlled polymerization of pMOS at 30 °C, and the molecular weights of the polymers (weight‐average molecular weight/number‐average molecular weight ~ 1.7) increase with conversion. These suspension polymerizations are initiated by the entry of sulfonic acid from the aqueous phase into the organic phase and proceed via reversible activation of the sulfonyl terminus by the Lewis acid. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2728–2733, 2000 |