Mechanism of Spatial and Temporal Control in Precision Cyclic Vinyl Polymer Synthesis by Lewis Pair Polymerization
AuthorsChen, Eugene Y.-X.
McGraw, Michael L.
Reilly, Liam T.
Clarke, Ryan W.
KAUST DepartmentChemical Science Program
KAUST Catalysis Center (KCC)
Physical Science and Engineering (PSE) Division
Embargo End Date2023-02-08
Permanent link to this recordhttp://hdl.handle.net/10754/675496
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AbstractIn typical cyclic polymer synthesis via ring-closure, chain growth and cyclization events are competing with each other, thus affording cyclic polymers with uncontrolled molecular weight or ring size and high dispersity. Here we uncover a mechanism by which Lewis pair polymerization (LPP) operates on polar vinyl monomers that allows the control of where and when cyclization takes place, thereby achieving spatial and temporal control to afford precision cyclic vinyl polymers or block copolymers with predictable molecular weight and low dispersity (~1.03). A combined experimental and theoretical study demonstrates that cyclization occurs only after all monomers have been consumed (when) via conjugate addition of the propagating chain end to the specific site of the initiating chain end (where), allowing the cyclic polymer formation steps to be regulated and executed with precision in space and time.
CitationChen, McGraw, M. L., Reilly, L. T., Clarke, R. W., Cavallo, L., & Falivene, L. (2022). Mechanism of Spatial and Temporal Control in Precision Cyclic Vinyl Polymer Synthesis by Lewis Pair Polymerization. Angewandte Chemie International Edition. Portico. https://doi.org/10.1002/anie.202116303
SponsorsWe gratefully acknowledge support by the U.S. National Science Foundation (NSF-1904962) for the work by MLM and LTR, and the U.S. Army Research Office (W911NF1810435) for the work by RWC. We thank Dr. Roy Geiss for his expertise and assistance with acquiring TEM images.