Revisiting the Anionic Polymerization of Methyl Ethacrylate

Justin G. Kennemur, Frank S. Bates, Marc A. Hillmyer

Research output: Contribution to journalArticlepeer-review

9 Scopus citations


Synthesis 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.

Original languageEnglish (US)
Article number1700282
JournalMacromolecular Chemistry and Physics
Issue number1
StatePublished - Jan 5 2018

Bibliographical note

Funding Information:
The authors wish to thank David Goldfeld for assistance with 13C NMR analysis. Funding for this project was provided, in part, by The Dow Chemical Company. J.G.K. wishes to acknowledge the FSU Materials and Energy Hiring Initiative and the Donors of the American Chemical Society Petroleum Research Fund (Grant No. 55378-DNI7) for partial support during the preparation of this manuscript. The authors also thank Javid Rzayev for helpful discussions.

Publisher Copyright:
© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim


  • anionic polymerization
  • block polymer
  • methyl ethacrylate
  • α-alkyl acrylate


Dive into the research topics of 'Revisiting the Anionic Polymerization of Methyl Ethacrylate'. Together they form a unique fingerprint.

Cite this