Title: Bio-Based Benzoxazine Monomer and Polymer Based on Vanillin and Difurfuryl Diamine

Authors: Mengwen Yu, Santosh K. Yadav, John J. La Scala and Giuseppe R. Palmese

DOI: 10.33599/nasampe/s.20.0206

Abstract: A type of bio-based benzoxazine monomer based on difurfuryl diamine (DFDA) obtained by the coupling of furfuryl amine using formaldehyde will be discussed. The benzoxazine monomer was synthesized by reacting DFDA with renewable phenolic vanillin and formaldehyde. This benzoxazine system was purified by precipitation to obtain solid powders that melt at 55°C to form low viscosity liquids that can be readily used to impregnate fiber reinforcements. Onset cure temperature is 163°C and the autocatalytic reaction behavior was observed. The resulting polybenzoxazine has about 244°C after post curing. It was found that the polybenzoxazine network containing high content of furan rings in the backbone provides the improvement of 800°C char yield compared with Bisphenol A (BPA) based polybenzoxaizines greater than 50% measured by TGA temperature ramps in an inert environment. This paper will discuss processing and thermal characteristics of this highly renewable material, which are useful for high temperature applications.

References: 1. Lligadas G, Tüzün A, Ronda JC, Galià M, Cádiz V. Polybenzoxazines: New players in the bio-based polymer arena. Polym Chem. 2014;5(23):6636-6644. doi:10.1039/c4py00914b 2. Ghosh NN, Kiskan B, Yagci Y. Polybenzoxazines-New high performance thermosetting resins: Synthesis and properties. Prog Polym Sci. 2007;32(11):1344-1391. doi:10.1016/j.progpolymsci.2007.07.002 3. Takeichi T, Kawauchi T, Agag T. High Performance Polybenzoxazines as a Novel Type of Phenolic Resin. Polym J. 2008;40(12):1121-1131. doi:10.1295/polymj.pj2008072 4. Ishida H, Agag T. Handbook of Benzoxazine Resins. Handb Benzoxazine Resins. 2011:740480. doi:10.1016/C2010-0-66598-9 5. Lochab B, Varma IK, Bijwe J. Thermal behaviour of cardanol-based benzoxazines: Monomers and polymers. J Therm Anal Calorim. 2010;102(2):769-774. doi:10.1007/s10973-010-0736-6 6. Sini NK, Bijwe J, Varma IK. Renewable benzoxazine monomer from Vanillin: Synthesis, characterization, and studies on curing behavior. J Polym Sci Part A Polym Chem. 2014;52(1):7-11. doi:10.1002/pola.26981 7. Shen X, Dai J, Liu Y, Liu X, Zhu J. Synthesis of high performance polybenzoxazine networks from bio-based furfurylamine: Furan vs benzene ring. Polymer (Guildf). 2017;122(March 2018):258-269. doi:10.1016/j.polymer.2017.06.075 8. Holfinger MS, Conner AH, Holm DR, Hill CG. Synthesis of Difurfuryl Diamines by the Acidic Condensation of Furfurylamine with Aldehydes and Their Mechanism of Formation. J Org Chem. 1995;60(6):1595-1598. doi:10.1021/jo00111a017 9. Wang C, Sun J, Liu X, Sudo A, Endo T. Synthesis and copolymerization of fully bio-based benzoxazines from guaiacol, furfurylamine and stearylamine. Green Chem. 2012;14(10):2799-2806. doi:10.1039/c2gc35796h 10. Ishida H, Sanders DP. Regioselectivity and network structure of difunctional alkyl-substituted aromatic amine-based polybenzoxazines. Macromolecules. 2000;33(22):8149-8157. doi:10.1021/ma991836t 11. Sini NK, Bijwe J, Varma IK. Thermal behaviour of bis-benzoxazines derived from renewable feed stock “vanillin.” Polym Degrad Stab. 2014;109:270-277. doi:10.1016/j.polymdegradstab.2014.07.015 12. Ishida H, Allen DJ. Physical and mechanical characterization of near-zero shrinkage polybenzoxazines. J Polym Sci Part B Polym Phys. 1996;34(6):1019-1030. doi:10.1002/(SICI)1099-0488(19960430)34:6<1019::AID-POLB1>3.0.CO;2-T

Conference: SAMPE 2020 | Virtual Series

Publication Date: 2020/06/01

SKU: TP20-0000000206

Pages: 7

Price: FREE