Photoinitiated Olefin Metathesis and Stereolithographic Printing of Polydicyclopentadiene

Recent progress in photoinitiated ring-opening metathesis polymerization (photoROMP) has enabled the lithographic production of patterned films from olefinic resins. Recently, we reported the use of a latent ruthenium catalyst (HeatMet) in combination with a photosensitizer (2-isopropylthioxanthone)...

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Bibliographic Details
Published in:Macromolecules 2022-09, Vol.55 (18), p.8273-8282
Main Authors: Leguizamon, Samuel C., Monk, Nicolas T., Hochrein, Madison T., Zapien, Elizabeth M., Yoon, Alana, Foster, Jeffrey C., Appelhans, Leah N.
Format: Article
Language:English
Subjects:
Additive manufacturing
Lithography
MATERIALS SCIENCE
Olefin metathesis
Photosensitizers
Ruthenium catalyst
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Summary:Recent progress in photoinitiated ring-opening metathesis polymerization (photoROMP) has enabled the lithographic production of patterned films from olefinic resins. Recently, we reported the use of a latent ruthenium catalyst (HeatMet) in combination with a photosensitizer (2-isopropylthioxanthone) to rapidly photopolymerize dicyclopentadiene (DCPD) formulations upon irradiation with UV light. While this prior work was limited in terms of catalyst and photosensitizer scope, a variety of alternative catalysts and photosensitizers are commercially available that could allow for tuning of thermomechanical properties, potlifes, activation rates, and irradiation wavelengths. Herein, 14 catalysts and 8 photosensitizers are surveyed for the photoROMP of DCPD and the structure–activity relationships of the catalysts examined. Properties relevant to stereolithography additive manufacturing (SLA AM)potlife, irradiation dose required to gel, conversionare characterized to develop catalyst and photosensitizer libraries to inform development of SLA AM resin systems. Two optimized catalyst/photosensitizer systems are demonstrated in the rapid SLA printing of complex, multidimensional pDCPD structures with microscale features under ambient conditions.
ISSN:0024-9297
1520-5835
DOI:10.1021/acs.macromol.2c01244