In order to break through the bottleneck of anionic polymerization, polar monomers such as methyl methacrylate (MMA), ethyl methacrylate, butyl methacrylate, and hexyl methacrylate are subjected to anionic polymerization at room temperature in tetrahydrofuran (THF) using potassium tert-butoxide (t-BuOK) as the initiator. The polymerization of alkyl methacrylates is studied by multidetector gel permeation chromatography, proton nuclear magnetic resonance (H-1-NMR) and C-13-NMR spectroscopy, and dynamic laser light scattering. It is found that t-BuOK can initiate the living anionic polymerization of polar alkyl methacrylate, and the polymerization conversion almost reaches up to 100%. t-BuOK exists into two kinds of agglomerates, whose hydrodynamic volumes are 10 and 80nm, respectively. t-BuOK in THF is similar to emulsion and has a critical active species concentration of about 0.0265molL(-1) and does not depend on how much t-BuOK is added. After the initiation of the polymerization, the large agglomerates of a loose and less regular structure that have occupied the main part of t-BuOK are greatly reduced, but they do not continue to decrease until they disappear according to the equilibrium theory. Similarly, the active chain after initiation also will not aggregate again. Furthermore, t-BuOK also has an active species with smaller average vibration size between cation and anion pairs, which can only initiate the polymerization of MMA with rather slow rate but cannot initiate other alkyl methacrylates. At last, because t-BuOK can make the dormant species caused by side reactions to be revived, the anionic polymerization of MMA could obtain a high yield. (c) 2019 Wiley Periodicals, Inc.