Revisiting the Anionic Polymerization of Methyl Ethacrylate

Abstract

AbstractSynthesis of poly(methyl ethacrylate), (PMEA), in tetrahydrofuran at −78 °C using anionic polymerization techniques results in high molar mass (>30 kg mol−1), low dispersity (1.3), and high conversion (>81%). The molar masses of a series of samples are consistent with values anticipated by the monomer‐to‐initiator ratio and conversion. These results represent a significant improvement to earlier reported attempts to prepare PMEA using anionic methods. Successful diblock polymerization of polystyrene‐block‐PMEA, (PS‐PMEA), and poly(4‐tert‐butylstyrene)‐block‐PMEA, (PtBS‐PMEA), is achieved through sequential anionic polymerization techniques with dispersities as low as 1.06 and segment molar fractions close to those targeted. Broad principal scattering peaks observed by small‐angle X‐ray scattering (SAXS) for symmetric PS‐PMEA at relatively high molar mass (39 kg mol−1) suggests an effective interaction parameter (χeff) that is smaller than for PS‐block‐poly(methyl methacrylate). On the other hand, PtBS‐PMEA block polymers form a well‐ordered morphology based on SAXS measurements and is attributable to the more hydrophobic PtBS segment. These results confirm the viability of PMEA as a new constituent in the expanding suite of polymers suitable for preparing nanostructured block polymers.