Title: Carbon Aerogels from Furan-Based Polybenzoxazine Precursors
Authors: Michael J. Chauby, Stephanie L. Vivod, Sadeq Malakooti, Giuseppe R. Palmese
DOI: 10.33599/nasampe/s.24.0055
Abstract: Polymer aerogels typically have physical properties that consist of high internal surface area (500-850m2/g), nano-scale pore size (10-30 nm), and high porosity (<97%), which lend to very low density and thermal conductivities. It is possible to enhance these materials by manipulating the chemistry of the underlying matrix. Polybenzoxazines are a thermosetting polymer that have low water retention, near zero volume shrinkage during cure, and high glass transition temperature making them ideal candidates to comprise the network of a polymer aerogel. When furan is introduced into the chemical structure, polybenzoxazines have been shown to have char yields exceeding 60% further expanding their use as the precursor network in carbon aerogels. Carbon aerogels have found applications in energy storage, adsorbents, and as thermal insulators due to their high electrical conductivity, chemical resistance, and the ability to withstand extreme temperatures of up to 3000 ℃ before degradation. In this study, a monofunctional furan-based benzoxazine with 4-hydroxybenzyl alcohol as the phenolic derivative and a difunctional furan-based benzoxazine with bisphenol A as the phenolic derivative was synthesized. Each monomer was thermally gelled at 140 ℃. Monomer weight concentration in dimethyl formamide (DMF) and its effect on volume shrinkage, surface area, and thermal stability with respect to the different furan-based polybenzoxazine chemistries was investigated. Carbon aerogels were fabricated from pyrolysis in a nitrogen atmosphere up to 1000 ℃ with a ramp rate of 10 ℃ min-1. The findings from this study provide a framework for the fabrication of carbon aerogels from furan-based polybenzoxazine precursors.
References: Lee J-H, Park S-J. Recent advances in preparations and applications of carbon aerogels: A review. Carbon N Y 2020;163:1–18. https://doi.org/10.1016/j.carbon.2020.02.073. [2]Hu L, He R, Lei H, Fang D. Carbon Aerogel for Insulation Applications: A Review. Int J Thermophys 2019;40:39. https://doi.org/10.1007/s10765-019-2505-5. [3]Gao X, Xing Z, Li Z, Dong X, Ju Z, Guo C. A review on recent advances in carbon aerogels: their preparation and use in alkali-metal ion batteries. New Carbon Materials 2020;35:486–507. https://doi.org/10.1016/S1872-5805(20)60504-2. [4]Allahbakhsh A, Bahramian AR. Self-assembled and pyrolyzed carbon aerogels: an overview of their preparation mechanisms, properties and applications. Nanoscale 2015;7:14139–58. https://doi.org/10.1039/C5NR03855C. [5]Pandey AP, Bhatnagar A, Shukla V, Soni PK, Singh S, Verma SK, et al. Hydrogen storage properties of carbon aerogel synthesized by ambient pressure drying using new catalyst triethylamine. Int J Hydrogen Energy 2020;45:30818–27. https://doi.org/10.1016/j.ijhydene.2020.08.145. [6]Geng S, Maennlein A, Yu L, Hedlund J, Oksman K. Monolithic carbon aerogels from bioresources and their application for CO2 adsorption. Microporous and Mesoporous Materials 2021;323:111236. https://doi.org/10.1016/j.micromeso.2021.111236. [7]Pekala R. Low density, resorcinol-formaldehyde aerogels, 1991. [8]Chriti D, Raptopoulos G, Papastergiou M, Paraskevopoulou P. Millimeter-Size Spherical Polyurea Aerogel Beads with Narrow Size Distribution. Gels 2018;4:66. https://doi.org/10.3390/gels4030066. [9]Saeed AM, Rewatkar PM, Majedi Far H, Taghvaee T, Donthula S, Mandal C, et al. Selective CO2 Sequestration with Monolithic Bimodal Micro/Macroporous Carbon Aerogels Derived from Stepwise Pyrolytic Decomposition of Polyamide-Polyimide-Polyurea Random Copolymers. ACS Appl Mater Interfaces 2017;9:13520–36. https://doi.org/10.1021/acsami.7b01910. [10]Chidambareswarapattar C, Xu L, Sotiriou-Leventis C, Leventis N. Robust monolithic multiscale nanoporous polyimides and conversion to isomorphic carbons. RSC Adv 2013;3:26459. https://doi.org/10.1039/c3ra43717e. [11]Biesmans G, Mertens A, Duffours L, Woignier T, Phalippou J. Polyurethane based organic aerogels and their transformation into carbon aerogels. J Non Cryst Solids 1998;225:64–8. https://doi.org/10.1016/S0022-3093(98)00010-6. [12]Ishida H. Overview and historical background of polybenzoxazine research. Handbook of Benzoxazine Resins, Elsevier; 2011, p. 3–81. https://doi.org/10.1016/B978-0-444-53790-4.00046-1. [13]Rimdusit S, Jubsilp C, Tiptipakorn S. Introduction to Commercial Benzoxazine and Their Unique Properties, 2013, p. 1–27. https://doi.org/10.1007/978-981-4451-76-5_1. [14]Leventis N, Donthula S. HCl-Catalyzed Polymerization of Benzoxazine and Chemical Transformations Along Pyrolysis to Microporous Carbons. Advanced and Emerging Polybenzoxazine Science and Technology, Elsevier; 2017, p. 673–95. https://doi.org/10.1016/B978-0-12-804170-3.00034-2. [15]Malakooti S, Qin G, Mandal C, Soni R, Taghvaee T, Ren Y, et al. Low-Cost, Ambient-Dried, Superhydrophobic, High Strength, Thermally Insulating, and Thermally Resilient Polybenzoxazine Aerogels. ACS Appl Polym Mater 2019;1:2322–33. https://doi.org/10.1021/acsapm.9b00408. [16]Mahadik-Khanolkar S, Donthula S, Sotiriou-Leventis C, Leventis N. Polybenzoxazine Aerogels. 1. High-Yield Room-Temperature Acid-Catalyzed Synthesis of Robust Monoliths, Oxidative Aromatization, and Conversion to Microporous Carbons. Chemistry of Materials 2014;26:1303–17. https://doi.org/10.1021/cm403483p. [17]Majedi Far H, Rewatkar PM, Donthula S, Taghvaee T, Saeed AM, Sotiriou‐Leventis C, et al. Exceptionally High CO2 Adsorption at 273 K by Microporous Carbons from Phenolic Aerogels: The Role of Heteroatoms in Comparison with Carbons from Polybenzoxazine and Other Organic Aerogels. Macromol Chem Phys 2019;220:1800333. https://doi.org/10.1002/macp.201800333. [18]Wang J, Liu W, Feng T. Furan-Based Benzoxazines. Advanced and Emerging Polybenzoxazine Science and Technology, Elsevier; 2017, p. 533–67. https://doi.org/10.1016/B978-0-12-804170-3.00028-7. [19]McKillip WJ. Chemistry of Furan Polymers, 1989, p. 408–23. https://doi.org/0.1021/bk-1989-0385.ch029. [20]Liu YL, Chou CI. High performance benzoxazine monomers and polymers containing furan groups. J Polym Sci A Polym Chem 2005;43:5267–82. https://doi.org/10.1002/pola.21023. [21]Li SF. Synthesis of benzoxazine-based phenolic resin containing furan groups. Chinese Chemical Letters 2010;21:868–71. https://doi.org/10.1016/j.cclet.2010.01.007. [22]Yang R, Han M, Hao B, Zhang K. Biobased high-performance tri-furan functional bis-benzoxazine resin derived from renewable guaiacol, furfural and furfurylamine. Eur Polym J 2020;131:109706. https://doi.org/10.1016/j.eurpolymj.2020.109706. [23]Thirukumaran P, Shakila Parveen A, Sarojadevi M. Synthesis and Copolymerization of Fully Biobased Benzoxazines from Renewable Resources. ACS Sustain Chem Eng 2014;2:2790–801. https://doi.org/10.1021/sc500548c.
Conference: SAMPE 2024
Publication Date: 2024/05/20
SKU: TP24-0000000055
Pages: 10
Price: $20.00
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