Compounded Interplay of Kinetic and Thermodynamic Control over Comonomer Sequences by Lewis Pair Polymerization

Liam T. Reilly, Michael L. McGraw, Francesca D. Eckstrom, Ryan W. Clarke, Kevin A. Franklin, Eswara Rao Chokkapu, Luigi Cavallo, Laura Falivene, Eugene Y.-X. Chen

Research output: Contribution to journalArticlepeer-review

10 Scopus citations


The design of facile synthetic routes to well-defined block copolymers (BCPs) from direct polymerization of one-pot comonomer mixtures, rather than traditional sequential additions, is both fundamentally and technologically important. Such synthetic methodologies often leverage relative monomer reactivity toward propagating species exclusively and therefore are rather limited in monomer scope and control over copolymer structure. The recently developed compounded sequence control (CSC) by Lewis pair polymerization (LPP) utilizes synergistically both thermodynamic (Keq) and kinetic (kp) differentiation to precisely control BCP sequences and suppress tapering and misincorporation errors. Here, we present an in-depth study of CSC by LPP, focusing on the complex interplay of the fundamental Keq and kp parameters, which enable the unique ability of CSC-LPP to precisely control comonomer sequences across a variety of polar vinyl monomer classes. Individual Lewis acid equilibrium and polymerization rate parameters of a range of commercially relevant monomers were experimentally quantified, computationally validated, and rationalized. These values allowed for the judicious design of copolymerizations which probed multiple hypotheses regarding the constructive vs conflicting nature of the relationship between Keq and kp biases, which arise during CSC-LPP of comonomer mixtures. These relationships were thoroughly explored and directly correlated with resultant copolymer microstructures. Several examples of higher-order BCPs are presented, further demonstrating the potential for materials innovation offered by this methodology.
Original languageEnglish (US)
JournalJournal of the American Chemical Society
StatePublished - Dec 15 2022

Bibliographical note

KAUST Repository Item: Exported on 2022-12-19
Acknowledgements: We gratefully acknowledge support by the U.S. National Science Foundation (NSF-1904962). We also acknowledge Dr. Roy Geiss for his help in acquiring the TEM images.

ASJC Scopus subject areas

  • Biochemistry
  • Colloid and Surface Chemistry
  • General Chemistry
  • Catalysis


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