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Processable Enediyne Resins and the High Yielding Glassy Carbons Derived Therefrom


Title: Processable Enediyne Resins and the High Yielding Glassy Carbons Derived Therefrom

Authors: Ernesto I. Borrego, Behzad Farajidizaji, Hossein Toghiani, Charles U. Pittman, Jr., Dennis W. Smith Jr.

DOI: 10.33599/nasampe/s.21.0618

Abstract: High temperature polynaphthalene networks derived via the step-growth thermal cyclopolymerization of bis-o-diynylarene (BODA) monomers have previously been shown to produce unprecedented high yielding glassy carbons upon pyrolysis at 1000°C. In our current studies to expand the processability parameters of the BODA approach for carbon-fiber matrix composite and carbon-carbon composite applications, we have introduced mono-o-diynylarene (MODA) co-monomers to control reactivity, branching, and ultimate crosslink density for specific pre- and post-carbonization applications. As a special class of enediynes, the MODA monomers were prepared in a single step from the Sonogashira coupling of terminal alkynes with diiodobenzene to yield enediynes of varying terminal substitution. Their cyclopolymerization with BODA are shown here to yield polymers with controlled molecular weight, viscosity, and latent enediyne reactivity. This work seeks to establish BODA-MODA copolymers which are amenable to current composite processing limits, improve mechanical properties, and which retain high temperature properties including extremely high (>75 %) carbon yields.

References: 1. Chung, D.D.L., 7 - Carbon-Matrix Composites, in Carbon Composites (Second Edition). 2017, Butterworth-Heinemann. p. 387-466. 2. Economy, J., H. Jung, and T. Gogeva, A one-step process for fabrication of carbon-carbon composites. Carbon, 1992. 30(1): p. 81-85. 3. Raunija, T.S.K., et al., Preparation and process optimization of randomly oriented C/C composites by a novel method. New Carbon Materials, 2018. 33(5): p. 423-433. 4. Smith, D.W., et al., Polynaphthalene Networks from Bisphenols. Journal of the American Chemical Society, 1998. 120(35): p. 9078-9079. 5. Smith Jr., D.W., et al., Polyarylene Networks via Bergman Cyclopolymerization of Bis-ortho-diynyl Arenes. Advanced Functional Materials, 2007. 17(8): p. 1237-1246. 6. Martin, S.J., et al., Development of a Low-Dielectric-Constant Polymer for the Fabrication of Integrated Circuit Interconnect. Advanced Materials, 2000. 12(23): p. 1769-1778. 7. Shah, H.V., et al., Bis-o-diynylarene (BODA) Derived Polynaphthalenes as Precursors to Glassy Carbon Microstructures. Chemistry of Materials, 1999. 11(10): p. 2623-2625. 8. Zengin, H. and D.W. Smith, Bis-ortho-diynylarene polymerization as a route to solid and hollow carbon fibers. Journal of Materials Science, 2007. 42(12): p. 4344-4349. 9. Perpall, M.W., et al., Novel Network Polymer for Templated Carbon Photonic Crystal Structures. Langmuir, 2003. 19(18): p. 7153-7156. 10. Yang, X., et al., Synthesis of Ultrathin Mesoporous Carbon through Bergman Cyclization of Enediyne Self-Assembled Monolayers in SBA-15. Langmuir, 2010. 26(13): p. 11244-11248. 11. Iacono, S.T., et al., Carbonization and thermal expansion of glassy carbon derived from bis-ortho-diynylarenes. Carbon, 2007. 45(5): p. 931-935. 12. Hay, A., Communications- Oxidative Coupling of Acetylenes. The Journal of Organic Chemistry, 1960. 25(7): p. 1275-1276. 13. Neenan, T.X. and G.M. Whitesides, Synthesis of high carbon materials from acetylenic precursors. Preparation of aromatic monomers bearing multiple ethynyl groups. The Journal of Organic Chemistry, 1988. 53(11): p. 2489-2496. 14. Bergman, R.G., Reactive 1,4-dehydroaromatics. Accounts of Chemical Research, 1973. 6(1): p. 25-31. 15. John, J.A. and J.M. Tour, Synthesis of Polyphenylenes and Polynaphthalenes by Thermolysis of Enediynes and Dialkynylbenzenes. Journal of the American Chemical Society, 1994. 116(11): p. 5011-5012. 16. Sastri, S.B., et al., Studies on cure chemistry of new acetylenic resins. Macromolecules, 1993. 26(23): p. 6171-6174. 17. Rule, J.D., S.R. Wilson, and J.S. Moore, Radical Polymerization Initiated by Bergman Cyclization. Journal of the American Chemical Society, 2003. 125(43): p. 12992-12993. 18. Gerstel, P. and C. Barner-Kowollik, RAFT Mediated Polymerization of Methyl Methacrylate Initiated by Bergman Cyclization: Access to High Molecular Weight Narrow Polydispersity Polymers. Macromolecular Rapid Communications, 2011. 32(5): p. 444-450. 19. Zhu, B., et al., Formation of polymeric nanoparticles via Bergman cyclization mediated intramolecular chain collapse. Journal of Materials Chemistry, 2011. 21(8): p. 2679-2683. 20. Cheng, X., et al., Synthesis of Novel “Rod−Coil” Brush Polymers with Conjugated Backbones through Bergman Cyclization. Macromolecules, 2010. 43(2): p. 909-913. 21. Sun, Q., et al., On-Surface Formation of One-Dimensional Polyphenylene through Bergman Cyclization. Journal of the American Chemical Society, 2013. 135(23): p. 8448-8451. 22. Wang, Y., S. Chen, and A. Hu, Construction of Polyarylenes with Various Structural Features via Bergman Cyclization Polymerization. Top Curr Chem (Cham), 2017. 375(3): p. 60. 23. Xiao, Y. and A. Hu, Bergman Cyclization in Polymer Chemistry and Material Science. Macromolecular Rapid Communications, 2011. 32(21): p. 1688-1698. 24. Ma, X., et al., Functionalization of Pristine Graphene with Conjugated Polymers through Diradical Addition and Propagation. Chemistry – An Asian Journal, 2012. 7(11): p. 2547-2550. 25. Rettenbacher, A.S., et al., Radical Addition of a Conjugated Polymer to Multilayer Fullerenes (Carbon Nano-onions). Chemistry of Materials, 2007. 19(6): p. 1411-1417. 26. Ma, J., et al., Functionalization of multiwalled carbon nanotubes with polyesters via bergman cyclization and “grafting from” strategy. Journal of Polymer Science Part A: Polymer Chemistry, 2010. 48(23): p. 5541-5548. 27. Ma, J., et al., Covalent surface functionalization of multiwalled carbon nanotubes through bergman cyclization of enediyne-containing dendrimers. Journal of Polymer Science Part A: Polymer Chemistry, 2011. 49(18): p. 3951-3959

Conference: SAMPE NEXUS 2021

Publication Date: 2021/06/29

SKU: TP21-0000000618

Pages: 9

Price: FREE

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