Tricyclononenes and tricyclononadienes as efficient monomers for controlled ROMP: understanding structure–propagation rate relationships and enabling facile post-polymerization modification

Kilgallon, Landon J.; McFadden, Timothy P.; Sigman, Matthew S.; Johnson, Jeremiah A.

doi:10.1039/d4sc01986e

Tricyclononenes and tricyclononadienes as efficient monomers for controlled ROMP: understanding structure–propagation rate relationships and enabling facile post-polymerization modification

Journal Article · Wed May 22 00:00:00 UTC 2024 · Chemical Science

DOI:https://doi.org/10.1039/d4sc01986e· OSTI ID:2352764

^[1]; ^[2]; Sigman, Matthew S. ^[2]; ^[3]

Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Univ. of Utah, Salt Lake City, UT (United States)
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States); Broad Institute of MIT and Harvard, Cambridge, MA (United States)

Grubbs 3rd-generation (G3) pre-catalyst-initiated ring-opening metathesis polymerization (ROMP) remains an indispensable tool in the polymer chemist's toolbox. Tricyclononenes (TCN) and tricyclononadienes (TCND) represent under-explored classes of monomers for ROMP that have the potential to both advance fundamental knowledge (e.g., structure-polymerization kinetics relationships) and serve as practical tools for the polymer chemist (e.g., post-polymerization functionalization). In this work, a library of TCN and TCND imides, monoesters, and diesters, along with their exo-norbornene counterparts, were synthesized to compare their behaviors in G3-initiated ROMP. Real-time ¹H NMR was used to study their polymerization kinetics; propagation rates (k_p) were extracted for each monomer. To understand the relationships between monomer structure and ROMP propagation rates, density functional theory methods were used to calculate a variety of electronic and steric parameters for each monomer. While electronic parameters (e.g., HOMO energy levels) correlated positively with the measured k_p values, steric parameters generally gave improved correlations, which indicates that monomer size and shape are better predictors for k_p than electronic parameters for this data set. Furthermore, the TCND diester—which contains an electron-deficient cyclobutene that is resistant to ROMP—and its polymer p(TCND) are shown to be highly reactive toward DBU-catalyzed conjugate addition reactions with thiols, providing a protecting- and activating-group free strategy for post-polymerization modification.

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Research Organization:: Univ. of Illinois at Urbana-Champaign, IL (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0023457

OSTI ID:: 2352764

Alternate ID(s):: OSTI ID: 2472280

Journal Information:: Chemical Science, Journal Name: Chemical Science Journal Issue: 22 Vol. 15; ISSN 2041-6520

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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