Initiating Mechanism of the Anionic Polymerization of Methacrylates with t‐BuOK and the Synthesis of ABA Type Triblock Copolymers.

Using potassium tert‐butoxide (t‐BuOK) as initiator, anionic polymerization and copolymerization of the methacrylate monomers are carried out in tetrahydrofuran at 0 °C or above. The polymers are characterized by gel permeation chromatography (GPC), proton nuclear magnetic resonance (1H‐NMR), Fourier transform infrared (FTIR), and dynamic mechanical analyzer (DMA). There is a critical concentration of the active species in t‐BuOK, above which no matter how much more t‐BuOK is added, it has no initiation activity. Among the active species of t‐BuOK, the main part possesses large average vibration distance between anion–cation pairs, which can initiate all methacrylate monomers in this study. While another part of the active species possesses the small average vibration distance, which can only initiate the polymerization of methyl methacrylate at slow rate. It provides an supporting evidence for the "channel idea" proposed previously. Finally, poly(methyl methacrylate)‐b‐poly(lauryl methacrylate)‐b‐poly(methyl methacrylate) (PMMA‐b‐PLMA‐b‐PMMA) three‐block copolymer is synthesized. This study paves the way for the synthesis of thermoplastic elastomers with full polar monomers and full saturated chains by anionic polymerization. [ABSTRACT FROM AUTHOR]