Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis

Suslick, Benjamin A.; Alzate-Sanchez, Diego M.; Moore, Jeffrey S.

doi:10.1021/acs.macromol.2c01654

Scalable Frontal Oligomerization: Insights from Advanced Mass Analysis

Journal Article · Thu Sep 15 00:00:00 EDT 2022 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.2c01654· OSTI ID:2339603

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University of Illinois at Urbana-Champaign, IL (United States); EFRC REMAT, University of Illinois Urbana-Champaign
University of Illinois at Urbana-Champaign, IL (United States)

Linear oligomers of dicyclopentadiene (DCPD) are reactive precursors for thermoplastic and thermoset materials. Unlike the foul-smelling parent monomer, oligomers composed of DCPD are odorless. With appropriate modification of the end-group or backbone chemistry, telechelic DCPD oligomers have potential utility as cross-linkers and as macromonomer precursors for block and graft copolymers. Most existing methods to produce oligo-DCPD, however, require solvent, are relatively slow, and necessitate air-free techniques. Here we show that frontal ring-opening metathesis oligomerization (FROMO) of neat DCPD and other norbornene derivatives rapidly generates hundreds of grams of material in minutes with catalyst loadings of 0.5 mM. This energy-efficient catalytic process utilizes the heat generated by the reaction to self-propagate oligomerization throughout the liquid monomer. FROMO employs a terminal olefin (e.g., styrene) in which a cross-metathesis reaction (i.e., chain transfer) competes with ring-opening metathesis (i.e., propagation). Kendrick mass analysis enables rapid identification and assignment of all the chain-end types present and quantifies the degree of branching resulting from the infrequent cyclopentene ring-opening reaction. This analytical technique also detects oligomer species derived from trace impurities in the monomer or chain-transfer agent that are otherwise difficult to observe with other characterization methods. Here, the obtained oligomers possess well-defined chain-ends and molecular weight distributions.

View Accepted Manuscript (DOE)

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

Sponsoring Organization:: USDOE Advanced Research Projects Agency - Energy (ARPA-E)

Grant/Contract Number:: SC0023457

OSTI ID:: 2339603

Alternate ID(s):: OSTI ID: 1978166

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 18 Vol. 55; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Anisotropic Foams via Frontal Polymerization Alzate‐Sanchez, Diego M.; Cencer, Morgan M.; Rogalski, Michael Advanced Materials, Vol. 34, Issue 8 https://doi.org/10.1002/adma.202105821	journal	January 2022
Heterotelechelic Polymers by Ring-Opening Metathesis and Regioselective Chain Transfer Liu, Peng; Yasir, Mohammad; Ruggi, Albert Angewandte Chemie International Edition, Vol. 57, Issue 4 https://doi.org/10.1002/anie.201708733	journal	December 2017
Catalytic Living Ring Opening Metathesis Polymerisation: The Importance of Ring Strain in Chain Transfer Agents Liu, Peng; Yasir, Mohammad; Kilbinger, Andreas F. M. Angewandte Chemie International Edition, Vol. 58, Issue 43 https://doi.org/10.1002/anie.201907921	journal	September 2019
Practical Ruthenium Catalysts for the Synthesis of Cyclic Olefin Oligomers, Polymers, and their Hydrogenated Derivatives Dumrath, Christa; Dumrath, Andreas; Neumann, Helfried ChemCatChem, Vol. 6, Issue 11 https://doi.org/10.1002/cctc.201402610	journal	October 2014
The use of mass defect in modern mass spectrometry Sleno, Lekha Journal of Mass Spectrometry, Vol. 47, Issue 2 https://doi.org/10.1002/jms.2953	journal	February 2012
Capabilities of the remainders of nominal Kendrick masses and the referenced Kendrick mass defects for copolymer ions Fouquet, T.; Cody, R. B.; Sato, H. Journal of Mass Spectrometry, Vol. 52, Issue 9 https://doi.org/10.1002/jms.3963	journal	August 2017
The Kendrick analysis for polymer mass spectrometry Fouquet, Thierry N. J. Journal of Mass Spectrometry, Vol. 54, Issue 12 https://doi.org/10.1002/jms.4480	journal	December 2019
Advances in the frontal ring opening metathesis polymerization of dicyclopentadiene Ruiu, Andrea; Sanna, Davide; Alzari, Valeria Journal of Polymer Science Part A: Polymer Chemistry, Vol. 52, Issue 19 https://doi.org/10.1002/pola.27301	journal	July 2014
Effect of limonene on the frontal ring opening metathesis polymerization of dicyclopentadiene Alzari, Valeria; Nuvoli, Daniele; Sanna, Davide Journal of Polymer Science Part A: Polymer Chemistry, Vol. 54, Issue 1 https://doi.org/10.1002/pola.27776	journal	August 2015
Synthesis and thermal properties of linear polydicyclopentadiene via ring-opening metathesis polymerization with a third generation grubbs-type ruthenium-alkylidene complex Steese, Nicholas D.; Barvaliya, Dhruv; Poole, Xavier D. Journal of Polymer Science Part A: Polymer Chemistry, Vol. 56, Issue 4 https://doi.org/10.1002/pola.28909	journal	November 2017
Mathematical tools in analytical mass spectrometry Meija, Juris Analytical and Bioanalytical Chemistry, Vol. 385, Issue 3 https://doi.org/10.1007/s00216-006-0298-4	journal	March 2006
Manufacturing Aspects of Advanced Polymer Composites for Automotive Applications Friedrich, Klaus; Almajid, Abdulhakim A. Applied Composite Materials, Vol. 20, Issue 2 https://doi.org/10.1007/s10443-012-9258-7	journal	February 2012
The polymerization of dicyclopentadiene: an investigation of mechanism Davidson, T. A.; Wagener, K. B. Journal of Molecular Catalysis A: Chemical, Vol. 133, Issue 1-2, p. 67-74 https://doi.org/10.1016/S1381-1169(98)00091-0	journal	July 1998
Analysis of curing behavior of endo-dicyclopentadiene using different amounts of decelerator solution Yoo, Hyeong Min; Jeon, JI Ho; Li, Mei-Xian Composites Part B: Engineering, Vol. 161 https://doi.org/10.1016/j.compositesb.2018.12.068	journal	March 2019
Frontal vs. bulk polymerization of fiber-reinforced polymer-matrix composites Vyas, S.; Zhang, X.; Goli, E. Composites Science and Technology, Vol. 198 https://doi.org/10.1016/j.compscitech.2020.108303	journal	September 2020
A Mass Scale Based on CH ₂ = 14.0000 for High Resolution Mass Spectrometry of Organic Compounds. Kendrick, Edward. Analytical Chemistry, Vol. 35, Issue 13 https://doi.org/10.1021/ac60206a048	journal	December 1963
First Gut Instincts Are Always Right: The Resolution Required for a Mass Defect Analysis of Polymer Ions Can Be as Low as Oligomeric Fouquet, Thierry; Satoh, Takaya; Sato, Hiroaki Analytical Chemistry, Vol. 90, Issue 4 https://doi.org/10.1021/acs.analchem.7b04518	journal	January 2018
“Reverse Kendrick Mass Defect Analysis”: Rotating Mass Defect Graphs to Determine Oligomer Compositions for Homopolymers Cody, Robert B.; Fouquet, Thierry Analytical Chemistry, Vol. 90, Issue 21 https://doi.org/10.1021/acs.analchem.8b03413	journal	October 2018
Frontal Polymerization of Dicyclopentadiene: A Numerical Study Goli, Elyas; Robertson, Ian D.; Geubelle, Philippe H. The Journal of Physical Chemistry B, Vol. 122, Issue 16 https://doi.org/10.1021/acs.jpcb.7b12316	journal	April 2018
Cross-Linking Agents for Enhanced Performance of Thermosets Prepared via Frontal Ring-Opening Metathesis Polymerization Ivanoff, Douglas G.; Sung, Jaeuk; Butikofer, Sydney M. Macromolecules, Vol. 53, Issue 19 https://doi.org/10.1021/acs.macromol.0c01530	journal	September 2020
Survey of Catalysts for Frontal Ring-Opening Metathesis Polymerization Suslick, Benjamin A.; Stawiasz, Katherine J.; Paul, Justine E. Macromolecules, Vol. 54, Issue 11 https://doi.org/10.1021/acs.macromol.1c00566	journal	May 2021
Storable, Dual-Component Systems for Frontal Ring-Opening Metathesis Polymerization Suslick, Benjamin A.; Yazdani, Aliza N.; Cencer, Morgan M. Macromolecules, Vol. 55, Issue 13 https://doi.org/10.1021/acs.macromol.2c00775	journal	June 2022
Photothermal Initiation of Frontal Polymerization Using Carbon Nanoparticles Dean, Leon M.; Ravindra, Amogha; Guo, Allen X. ACS Applied Polymer Materials, Vol. 2, Issue 11 https://doi.org/10.1021/acsapm.0c00726	journal	August 2020
Production and Dynamic Mechanical Analysis of Macro-Scale Functionalized Polydicyclopentadiene Objects Facilitated by Rational Synthesis and Reaction Injection Molding Cuthbert, Tyler J.; Li, Tong; Wulff, Jeremy E. ACS Applied Polymer Materials, Vol. 1, Issue 9 https://doi.org/10.1021/acsapm.9b00571	journal	August 2019
Spontaneous Patterning during Frontal Polymerization Lloyd, Evan M.; Feinberg, Elizabeth C.; Gao, Yuan ACS Central Science, Vol. 7, Issue 4 https://doi.org/10.1021/acscentsci.1c00110	journal	March 2021
Rapid Synthesis of Elastomers and Thermosets with Tunable Thermomechanical Properties Dean, Leon M.; Wu, Qiong; Alshangiti, Omar ACS Macro Letters, Vol. 9, Issue 6 https://doi.org/10.1021/acsmacrolett.0c00233	journal	May 2020
Photoexcitation of Grubbs’ Second-Generation Catalyst Initiates Frontal Ring-Opening Metathesis Polymerization Stawiasz, Katherine J.; Paul, Justine E.; Schwarz, Kevin J. ACS Macro Letters, Vol. 9, Issue 11 https://doi.org/10.1021/acsmacrolett.0c00486	journal	October 2020
A Single Functionalization Agent for Heterotelechelic ROMP Polymers Yasir, Mohammad; Singh, Manvendra; Kilbinger, Andreas F. M. ACS Macro Letters, Vol. 11, Issue 6 https://doi.org/10.1021/acsmacrolett.2c00234	journal	June 2022
Photoredox-Initiated Frontal Ring-Opening Metathesis Polymerization Stawiasz, Katherine J.; Wendell, Chloe I.; Suslick, Benjamin A. ACS Macro Letters, Vol. 11, Issue 6 https://doi.org/10.1021/acsmacrolett.2c00248	journal	May 2022
Frontal Ring-Opening Metathesis Polymerization of Exo-Dicyclopentadiene for Low Catalyst Loadings Robertson, Ian D.; Pruitt, Emmy L.; Moore, Jeffrey S. ACS Macro Letters, Vol. 5, Issue 5 https://doi.org/10.1021/acsmacrolett.6b00227	journal	April 2016
Alkyl Phosphite Inhibitors for Frontal Ring-Opening Metathesis Polymerization Greatly Increase Pot Life Robertson, Ian D.; Dean, Leon M.; Rudebusch, Gabriel E. ACS Macro Letters, Vol. 6, Issue 6 https://doi.org/10.1021/acsmacrolett.7b00270	journal	May 2017
Frontal Ring-Opening Metathesis Copolymerization: Deviation of Front Velocity from Mixing Rules Liu, Huiying; Wei, Haibing; Moore, Jeffrey S. ACS Macro Letters, Vol. 8, Issue 7 https://doi.org/10.1021/acsmacrolett.9b00367	journal	June 2019
Curing Kinetics and Mechanical Properties of endo -Dicyclopentadiene Synthesized Using Different Grubbs’ Catalysts Yang, Guang; Lee, Jong Keun Industrial & Engineering Chemistry Research, Vol. 53, Issue 8 https://doi.org/10.1021/ie403285q	journal	February 2014
A General Model for Selectivity in Olefin Cross Metathesis Chatterjee, Arnab K.; Choi, Tae-Lim; Sanders, Daniel P. Journal of the American Chemical Society, Vol. 125, Issue 37 https://doi.org/10.1021/ja0214882	journal	September 2003
End Capping Ring-Opening Olefin Metathesis Polymerization Polymers with Vinyl Lactones Hilf, Stefan; Grubbs, Robert H.; Kilbinger, Andreas F. M. Journal of the American Chemical Society, Vol. 130, Issue 33 https://doi.org/10.1021/ja8022863	journal	July 2008
Metal-Free Preparation of Linear and Cross-Linked Polydicyclopentadiene Goetz, Adam E.; Boydston, Andrew J. Journal of the American Chemical Society, Vol. 137, Issue 24 https://doi.org/10.1021/jacs.5b03665	journal	June 2015
Adaptable Crosslinks in Polymeric Materials: Resolving the Intersection of Thermoplastics and Thermosets Scheutz, Georg M.; Lessard, Jacob J.; Sims, Michael B. Journal of the American Chemical Society, Vol. 141, Issue 41 https://doi.org/10.1021/jacs.9b07922	journal	September 2019
Frontal Ring-Opening Metathesis Polymerization of Dicyclopentadiene Mariani, Alberto; Fiori, Stefano; Chekanov, Yuri Macromolecules, Vol. 34, Issue 19 https://doi.org/10.1021/ma0106999	journal	September 2001
Synthesis of End-Functionalized Poly(norbornene)s via Ring-Opening Metathesis Polymerization Bielawski, Christopher W.; Benitez, Diego; Morita, Takeharu Macromolecules, Vol. 34, Issue 25 https://doi.org/10.1021/ma010878q	journal	November 2001
Polymerization of Dicyclopentadiene: A Tale of Two Mechanisms Davidson, T. A.; Wagener, K. B.; Priddy, D. B. Macromolecules, Vol. 29, Issue 2 https://doi.org/10.1021/ma950852x	journal	January 1996
Relative Reaction Rates of Olefin Substrates with Ruthenium(II) Carbene Metathesis Initiators¹ Ulman, Michael; Grubbs, Robert H. Organometallics, Vol. 17, Issue 12 https://doi.org/10.1021/om9710172	journal	May 1998
Recent advances in ring-opening metathesis polymerization, and application to synthesis of functional materials Sutthasupa, Sutthira; Shiotsuki, Masashi; Sanda, Fumio Polymer Journal, Vol. 42, Issue 12 https://doi.org/10.1038/pj.2010.94	journal	October 2010
Catalytic living ring-opening metathesis polymerization with Grubbs’ second- and third-generation catalysts Yasir, Mohammad; Liu, Peng; Tennie, Iris K. Nature Chemistry, Vol. 11, Issue 5 https://doi.org/10.1038/s41557-019-0239-4	journal	April 2019
Rapid energy-efficient manufacturing of polymers and composites via frontal polymerization Robertson, Ian D.; Yourdkhani, Mostafa; Centellas, Polette J. Nature, Vol. 557, Issue 7704 https://doi.org/10.1038/s41586-018-0054-x	journal	May 2018
Cleavable comonomers enable degradable, recyclable thermoset plastics Shieh, Peyton; Zhang, Wenxu; Husted, Keith E. L. Nature, Vol. 583, Issue 7817 https://doi.org/10.1038/s41586-020-2495-2	journal	July 2020
Key processes in ruthenium-catalysed olefin metathesis Nelson, David J.; Manzini, Simone; Urbina-Blanco, César A. Chemical Communications, Vol. 50, Issue 72 https://doi.org/10.1039/C4CC02515F	journal	January 2014
Ring-opening Metathesis Polymerisation derived poly(dicyclopentadiene) based materials Kovačič, Sebastijan; Slugovc, Christian Materials Chemistry Frontiers, Vol. 4, Issue 8 https://doi.org/10.1039/D0QM00296H	journal	January 2020
Curing Methods for Advanced Polymer Composites - A Review Abliz, Dilmurat; Duan, Yugang; Steuernagel, Leif Polymers and Polymer Composites, Vol. 21, Issue 6 https://doi.org/10.1177/096739111302100602	journal	July 2013
Decomposition of Ruthenium Olefin Metathesis Catalyst Jawiczuk, Magdalena; Marczyk, Anna; Trzaskowski, Bartosz Catalysts, Vol. 10, Issue 8 https://doi.org/10.3390/catal10080887	journal	August 2020

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