Photoinitiated thermoset polymerization through controlled release of metathesis catalysts encapsulated in poly(phthalaldehyde)

Davydovich, Oleg; Lewis, Josephine; Romero, Mikayla; Deitz, Julia; C'deBaca, Francesca; Schwartz, Jared M.; Engler, Anthony C.; Kohl, Paul A.; Leguizamon, Samuel C.; Jones, Brad H.

doi:10.1039/d4py00882k

Photoinitiated thermoset polymerization through controlled release of metathesis catalysts encapsulated in poly(phthalaldehyde)

Journal Article · Tue Nov 26 23:00:00 EST 2024 · Polymer Chemistry

DOI:https://doi.org/10.1039/d4py00882k· OSTI ID:2540241

^[1]; Lewis, Josephine ^[1]; Romero, Mikayla ^[1]; Deitz, Julia ^[1]; C'deBaca, Francesca ^[1]; Schwartz, Jared M. ^[2]; Engler, Anthony C. ^[3]; ^[2]; Leguizamon, Samuel C. ^[1]; ^[1]

Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)
Georgia Institute of Technology, Atlanta, GA (United States)
Louisiana State University, Baton Rouge, LA (United States)

Photoinitiated polymerization enables spatiotemporal control of reaction conditions and can thereby generate materials with high complexity while consuming minimal energy. Where ring opening metathesis polymerization (ROMP) is concerned, photo-activated processes are typically enabled by chemical inhibition of ruthenium carbenes via the careful design of complexed ligands such that photoactivation can proceed through an isomerization or ligand dissociation event. In this contribution, we have explored a new approach to photoinitiation of ROMP based on physical inhibition through microencapsulation and controlled release of metathesis catalysts. Micron-sized particles of poly(phthalaldehyde) (PPA), catalyst, and photoacid generator were fabricated by spray drying. The particles were dispersed in dicyclopentadiene monomer, after which polymerization was initiated through temperature or UV exposure, both inducing depolymerization of the PPA particles and in situ catalyst release. The monomer/particle dispersions were found to be stable and reproducibly polymerizable with 3 weeks of storage at room temperature. Furthermore, the dispersions can be used for both photo- and thermal-initiated frontal ROMP, yielding a polymerized thermoset of equivalent properties to conventional bulk- and frontally-polymerized analogues. In conclusion, this work will ultimately enable new manufacturing techniques for ROMP-based materials, due to the modular, easily tunable nature of the underlying initiating system and its unparalleled stability.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Laboratory Directed Research and Development (LDRD) Program

Grant/Contract Number:: NA0003525

OSTI ID:: 2540241

Report Number(s):: SAND--2025-03537J

Journal Information:: Polymer Chemistry, Journal Name: Polymer Chemistry Journal Issue: 1 Vol. 16; ISSN 1759-9954

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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