Title: Liquid Rubber Modification of Vinyl Ester Resins to Obtain Toughened Thermosets for Photolithography

Authors: Jaclyn A. McLaughlin, Giuseppe R. Palmese

DOI: 10.33599/nasampe/s.22.0693

Abstract: There exists a large demand for the fabrication of polymeric engineering parts by additive manufacturing. While many available thermoset photolithography resins achieve desirable performance capabilities, these systems commonly exhibit low fracture toughness due to their highly crosslinked structures. This limits the application of additively manufacture thermosets. A well-established method for toughening conventional thermosets is by secondary phase modification via functionally terminated butadiene-acrylonitrile (TBN) elastomers. However, due to poor compatibility with acrylate-based resins and high viscosity, these additives have yet to be implemented within photolithography resins. In this study, a low viscosity, bio-based, liquid rubber (Oct3) is added to photocurable vinyl ester resins and its toughening effect on printed thermosets was observed. The performance of printed thermosets modified with Oct3 is directly compared to thermosets containing vinyl-terminated butadiene acrylonitrile. Processable conditions were maintained when Oct3 was added to the base resin in various amounts (5-15 phr). Fracture toughness (KQ) of modified thermosets was observed to increase from 0.48 ± 0.01 MPa∙m1/2 to 0.83 ± 0.14 MPa∙m1/2 when 15 phr Oct3 was incorporated to the resin.

References: 1. “3D Printing Market Size, Share: Industry Report, 2021-2028.” 3D Printing Market Size, Share | Industry Report, 2021-2028, Grand View Research, Inc., May 2021, https://www.grandviewresearch.com/industry-analysis/3d-printing-industry-analysis. 2. “3D Printing Materials Market Size, Share & Industry Analysis, by Type (Plastics, Metals, Ceramics, and Others), by End-Users (Automotive, Aerospace & Defense, Industrial, Medical, and Others), and Regional Forecast, 2019-2026.” 3D Printing Materials Market Share | Industry Report, 2026, Apr. 2020, https://www.fortunebusinessinsights.com/3d-printing-material-market-102296. 3. Zaiee S., Palmese G.R. Journal of Polymer Science: Part B 1999; 37:725-744 4. Kuang, Xiao, et al. “High‐Speed 3D Printing of High‐Performance Thermosetting Polymers via Two‐Stage Curing.” Macromolecular Rapid Communications, vol. 39, no. 7, 2018, p. 1700809., https://doi.org/10.1002/marc.201700809. 5. Tu, Jianwei, et al. “Formulation of a Model Resin System for Benchmarking Processing-Property Relationships in High-Performance Photo 3D Printing Applications.” Materials, vol. 13, no. 18, 2020, p. 4109., https://doi.org/10.3390/ma13184109. 6. La Scala, John J., et al. “The Use of Bimodal Blends of Vinyl Ester Monomers to Improve Resin Processing and Toughen Polymer Properties.” Polymer, vol. 46, no. 9, 2005, pp. 2908–2921., https://doi.org/10.1016/j.polymer.2005.02.011. 7. Auad, M.L., Proia, M., Borrajo, J. et al. Rubber modified vinyl ester resins of different molecular weights. Journal of Materials Science 37, 4117–4126 (2002). https://doi.org/10.1023/A:1020031701950 8. Huang, Yan-Jyi, et al. “Toughening of Unsaturated Polyester Resins with Core–Shell Rubbers.” Journal of Applied Polymer Science, vol. 107, no. 2, 2007, pp. 939–950., https://doi.org/10.1002/app.25159. 9. Ahmadi, M., et al. “Rubber Modification of Unsaturated Polyester Resin with Core-Shell Rubber Particles: Effect of Shell Composition.” Polymer Engineering & Science, vol. 52, no. 9, 2012, pp. 1928–1937., https://doi.org/10.1002/pen.23154. 10. Wilson, Kristen S., and Joseph M. Antonucci. “Interphase Structure–Property Relationships in Thermoset Dimethacrylate Nanocomposites.” Dental Materials, vol. 22, no. 11, 2006, pp. 995–1001., https://doi.org/10.1016/j.dental.2005.11.022. 11. Su, Yu-Chieh, and Trong-Ming Don. “Morphology and Mechanical Properties of Dual-Curable Epoxyacrylate Hybrid Composites.” Journal of Applied Polymer Science, vol. 132, no. 15, 2014, https://doi.org/10.1002/app.41820. 12. Robinette, E.J., et al. “Toughening of Vinyl Ester Resin Using Butadiene-Acrylonitrile Rubber Modifiers.” Polymer, vol. 45, no. 18, 2004, pp. 6143–6154., https://doi.org/10.1016/j.polymer.2004.07.003. 13. Ullett, Jill S., and Richard P. Chartoff. “Toughening of Unsaturated Polyester and Vinyl Ester Resins with Liquid Rubbers.” Polymer Engineering and Science, vol. 35, no. 13, 1995, pp. 1086–1097., https://doi.org/10.1002/pen.760351304. 14. Auad, Maria L., et al. “Morphology of Rubber-Modified Vinyl Ester Resins Cured at Different Temperatures.” Journal of Applied Polymer Science, vol. 89, no. 1, 2003, pp. 274–283., https://doi.org/10.1002/app.12183. 15. Dreerman, E., et al. “Mechanical Behavior and Structure of Rubber Modified Vinyl Ester Resins.” Journal of Applied Polymer Science, vol. 72, no. 5, 1999, pp. 647–657., https://doi.org/10.1002/(sici)1097-4628(19990502)72:5<647::aid-app5>3.0.co;2-m. 16. Hu F., Yadav S.K., La Scala J.J., Throckmorton J., Palmese G.R., Journal of Applied Polymer Science, 2021;38:1-15. 17. Hu, F., La Scala J.J., Yadav S.K., Throckmorton J., Palmese G.R., Journal of Applied Polymer Science, 2021;38:1-20. 18. Yadav, Santosh K., et al. “Toughening Anhydride-Cured Epoxy Resins Using Fatty Alkyl-Anhydride-Grafted Epoxidized Soybean Oil.” ACS Omega, vol. 3, no. 3, 2018, pp. 2641–2651., https://doi.org/10.1021/acsomega.7b02042. 19. Palmese, G.R. (2016). TOUGHENING CROSS-LINKED THERMOSETS (US Patent No. 9394427 B2). https://patents.google.com/patent/US9394427B2/en. 20. CVC Thermoset Specialties. Capabilities & Product Selection Guide, Moorestown, NJ, 2015. 21. Pearson R. A. YAF. Journal of Materials Science 1991; 26:3828-3844. 22. Cohen, N. Revised Group Additivity Values for Enthalpies of Formation (at 298K) of Carbon-Hydrogen and Carbon-Hydrogen-Oxygen Compounds. NIST, 4 Sept. 1996, https://www.nist.gov/system/files/documents/srd/jpcrd516.pdf.

Conference: SAMPE 2022

Publication Date: 2022/05/23

SKU: TP22-0000000693

Pages: 14

Price: $28.00