Photoinitiated Olefin Metathesis and Stereolithographic Printing of Polydicyclopentadiene

Samuel C. Leguizamon; Nicolas T. Monk; Madison T. Hochrein; Elizabeth M. Zapien; Alana Yoon; Jeffrey C. Foster; Leah N. Appelhans

doi:10.1021/acs.macromol.2c01244

Photoinitiated Olefin Metathesis and Stereolithographic Printing of Polydicyclopentadiene

Samuel C. Leguizamon, Nicolas T. Monk, Madison T. Hochrein, Elizabeth M. Zapien, Alana Yoon, Jeffrey C. Foster, Leah N. Appelhans

Research output: Contribution to journal › Article › peer-review

18 Scopus citations

Abstract

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.

Original language	English
Pages (from-to)	8273-8282
Number of pages	10
Journal	Macromolecules
Volume	55
Issue number	18
DOIs	https://doi.org/10.1021/acs.macromol.2c01244
State	Published - Sep 27 2022
Externally published	Yes

Funding

We thank Brad H. Jones for their review of the manuscript. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the U.S. Department of Energy (DOE) or the U.S. Government. Sandia National Laboratories is a multimission laboratory managed and operated by the National Technology and Engineering Solutions of Sandia, LLC, a wholly owned subsidiary of Honeywell International, Inc., for the U.S. Department of Energy’s National Nuclear Security Administration under contract DE-NA-0003525.

Funders	Funder number
U.S. Department of Energy
National Nuclear Security Administration	DE-NA-0003525

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1021/acs.macromol.2c01244

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title = "Photoinitiated Olefin Metathesis and Stereolithographic Printing of Polydicyclopentadiene",

abstract = "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.",

author = "Leguizamon, {Samuel C.} and Monk, {Nicolas T.} and Hochrein, {Madison T.} and Zapien, {Elizabeth M.} and Alana Yoon and Foster, {Jeffrey C.} and Appelhans, {Leah N.}",

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AU - Yoon, Alana

AU - Foster, Jeffrey C.

AU - Appelhans, Leah N.

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Photoinitiated Olefin Metathesis and Stereolithographic Printing of Polydicyclopentadiene

Abstract

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UN SDGs

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