A General Autofluorescence Method to Characterize Polymerization Progress

López, Pía A.; Pham, Vy H. B.; Blum, Suzanne A.

doi:10.1002/ange.202304618

Title: A General Autofluorescence Method to Characterize Polymerization Progress

Journal Article · 12 June 2023 · Angewandte Chemie

DOI: https://doi.org/10.1002/ange.202304618 · OSTI ID:1984733

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Department of Chemistry University of California, Irvine Irvine CA 92697-2025 USA

Abstract An autofluorescence technique to characterize polymerization progress in real time/in line was developed, which functioned in the absence of typical fluorogenic groups on the monomer or polymer. The monomer dicyclopentadiene and polymer polydicyclopentadiene are hydrocarbons that lack traditional functional groups for fluorescence spectroscopy. Here, the autofluorescence of formulations containing this monomer and polymer during ruthenium‐catalyzed ring‐opening metathesis polymerization (ROMP) was harnessed for reaction monitoring. The methods fluorescence recovery after photobleaching (FRAP) and here‐developed fluorescence lifetime recovery after photobleaching (FLRAP) characterized polymerization progress in these native systems—without requiring exogenous fluorophore. (Auto)fluorescence lifetime recovery changes during polymerization correlated linearly to degree of cure, providing a quantitative link with reaction progress. These changing signals also provided relative rates of background polymerization, enabling comparison of 10 different catalyst‐inhibitor‐stabilized formulations. Multiple‐well analysis demonstrated suitability for future high‐throughput evaluation of formulations for thermosets. The central concept of the combined autofluorescence and FLRAP/FRAP method may be extendable to monitoring other polymerization reactions previously overlooked for lack of an obvious fluorescence handle.

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Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0016467

OSTI ID:: 1984733

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 29 Vol. 135; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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