Journal of Science  and Technology of Composites

Journal of Science and Technology of Composites

Structure-property relationship of cycloaliphatic epoxy resins: the role of epoxidized aliphatic ring in increasing mechanical properties

Document Type : Research Paper

Authors
Department of Polymer Engineering, Faculty of Materials and Manufacturing Technologies, Malek-Ashtar University of Technology, Tehran, Iran.
Abstract
Cycloaliphatic structure in epoxy resins can improve chemical, physical, mechanical and electrical properties. In order to investigate this issue, two cycloaliphatic epoxy resins, (bi-functional) and (tri-functional) were used and then their properties were investigated and compared with DGEBA epoxy resin which has an aromatic structure. All three resins were cured with m-Phenylenediamine and the properties of the cured resins were analyzed by DSC, DMTA and three-point bending analysis. According to the obtained results, the strength and flexural modulus and ILSS of the DGEBA sample were 60, 2600 and 116 MPa, respectively. Bi-functional cycloaliphatic epoxy resin has a limited increase in properties (59, 3700 and 123 MPa) due to the hydrogen bonds of ester groups, and the cycloaliphatic structure hanging in the network does not contribute much to the increase in properties. Meanwhile, the tri-functional epoxy resin, in addition to the role of hydrogen bonds of ester groups, has unique properties due to the correct placement of the cycloaliphatic structure in the cured network and the higher crosslinking density. If the cycloaliphatic structure is placed in polymer network with four links, through the change of conformation between the boat and chair forms or by stretching it, it dissipates the external energy entered into system and by increasing the fracture energy, it prevents the brittle fracture of cured resin. The strength, flexural modulus and ILSS of tri-functional cycloaliphatic resin were obtained as 82, 4300 and 173 MPa, respectively, which shows improvement of about 35, 70 and 50% compared to DGEBA epoxy resin.
Keywords

Subjects


[1]  Xia, Y., Zhang, D., Li, Z., Lin, H., Chen, X., Oliver, S., Shi, S. and Lei, L., “Toughness Modification of Cationic UV-Cured Cycloaliphatic Epoxy Resin by Hydroxyl Polymers with Different Structures,” European Polymer Journal, Vol. 127, p. 109594, 2020.
[2]  Lu, M., Liu, Y., Du, X., Zhang, S., Chen, G., Zhang, Q., Yao, S., Liang, L. and Lu, M., “Cure Kinetics and Properties of High Performance Cycloaliphatic Epoxy Resins Cured with Anhydride,” Industrial & Engineering Chemistry Research, Vol. 58, No. 16, pp. 6907–6918, 2019.
[3]  Ahmadi, M., Fattahi, H., Mortezaei, M. and Mirbagheri, S. M. J., “High Temperature Cyanate Ester/Carbon Fiber Composite with High ILSS Based on Synthesized 2,2’-Bis(4-cyanatophenyl) Propane Resin,” In Persian, Journal of Science and Technology of Composites, Vol. 11, No. 1, pp. 2419–2428, 2024.
[4]  Payamani, M., Fattahi, H. and Mortezaei, M., “Synthesis and Characterization of 4,4’-Bis(maleimido)diphenylmethane Resin and Evaluation of Its Curing Behavior in Blending with Epoxy,” In Persian, Iranian Journal of Polymer Science and Technology, Vol. 35, No. 4, pp. 339–352, 2022.
[5]  Xu, R., Meng, D., Sun, H., Zhou, J., Cheng, S. and Li, Z., “Synthesis and Properties of Cycloaliphatic Epoxy Resins Containing Imide and Diphenyl Sulfone,” High Performance Polymers, Vol. 31, No. 4, pp. 380–387, 2019.
[6]  Sivanesan, D., Seo, B., Lim, C.S., Kim, S. and Kim, H.G., “Trifunctional Cycloaliphatic Epoxy-Based Thermoset Polymers: Synthesis, Polymerization, and Characterization,” Polymer, Vol. 220, p. 123568, 2021.
[7]  Rafie, M., Mozaffari, S. M. and SalimiKenari, H., “Concentration Effect of Mcroencapsulated 1-Methyl Imidazole Curing Agent with Solid Epoxy Shell on Mechanical Properties of Epoxy Resin,” In Persian, Iranian Journal of Polymer Science and Technology, Vol. 34, No. 6, pp. 523–532, 2022.
[8]  Ognibene, G., Mannino, S., Fragalà, M.E. and Cicala, G., “Trifunctional Epoxy Resin Composites Modified by Soluble Electrospun Veils: Effect on the Viscoelastic and Morphological Properties,” Materials, Vol. 11, No. 3, p. 405, 2018.
[9]  Liu, Y., Lin, Y., Wang, Y., Wu, K., Cao, B. and Wang, L., “Simultaneously Improving Toughness and Hydrophobic Properties of Cycloaliphatic Epoxy Resin Through Silicone Prepolymer,” Journal of Applied Polymer Science, Vol. 139, No. 32, 2022.
[10] Jahani, M., Fatahi, H. and Mortezaeei, M., “Effect of Aromatic Amine Structure as a Curing Agent on Molecular Packing and Mechanical Properties of Cured Epoxy Resin,” In Persian, Iranian Journal of Polymer Science and Technology, Vol. 32, No. 3, pp. 267–276, 2019.
[11] Bordbar, M.S., Salimi, A. and Karimi, M., “Dispersion of Glycidyl POSS-modified Silica Nanoparticles in Epoxy,” In Persian, Iranian Journal of Polymer Science and Technology, Vol. 34, No. 2, pp. 131–142, 2021.
[12] Zhang, Q., Wu, J., Gao, L., Liu, T., Zhong, W., Sui, G., Zheng, G., Fang, W. and Yang, X., “Dispersion Stability of Functionalized MWCNT in the Epoxy–Amine System and its Effects on Mechanical and Interfacial Properties of Carbon Fiber Composites,” Materials & Design, Vol. 94, pp. 392–402, 2016.
[13] Hajebi, S., Payamani, M., Fattahi, H., Mortezaei, M. and Jalilolghadr, S., “Dual-Curing Epoxy Thermosets: Design, Curing, Properties and Applications,” Polymer Reviews, pp. 1–31, 2024.
[14] Meng, Z., Bessa, M.A., Xia, W., Kam Liu, W. and Keten, S., “Predicting the Macroscopic Fracture Energy of Epoxy Resins from Atomistic Molecular Simulations,” Macromolecules, Vol. 49, No. 24, pp. 9474–9483, 2016.
[15] Wan, J., Gan, B., Li, C., Molina-Aldareguia, J., Kalali, E.N., Wang, X. and Wang, D.Y., “A Sustainable, Eugenol-Derived Epoxy Resin with High Biobased Content, Modulus, Hardness and low Flammability: Synthesis, Curing Kinetics and Structure–Property Relationship,” Chemical Engineering Journal, Vol. 284, pp. 1080–1093, 2016.
[16] Wei, J., Ma, S., Yue, H., Wang, S. and Zhu, J., “Comparison of Hydrogenated Bisphenol A and Bisphenol A Epoxies: Curing Behavior, Thermal and Mechanical Properties, Shape Memory Properties,” Macromolecular Research, Vol. 26, No. 6, pp. 529–538, 2018.
[17] Suliga, A., Hamerton, I. and Viquerat, A., “Cycloaliphatic Epoxy-Based Hybrid Nanocomposites Reinforced with POSS or Nanosilica for Improved Environmental Stability in Low Earth Orbit,” Composites Part B: Engineering, Vol. 138, pp. 66–76, 2018.
[18] Santiago, D. and Serra, À., “Enhancement of Epoxy Thermosets with Hyperbranched and Multiarm Star Polymers: A Review,” Polymers, Vol. 14, No. 11, p. 2228, 2022.
[19] Li, X. and Yee, A.F., “Design of Mechanically Robust High-Tg Polymers: Mechanical Properties of Glassy Poly(ester carbonate)s with Cyclohexylene Rings in the Backbone,” Macromolecules, Vol. 37, No. 19, pp. 7231–7239, 2004.
[20] Li, Z., Yang, Y., Ma, L., Liu, H. and Zhang, X., “Shape Memory Epoxy Resin and its Composite with Good Shape Memory Performance and High Mechanical Strength,” Polymer Bulletin, Vol. 80, No. 2, pp. 1641–1655, 2023.
[21] Acebo, C., Ramis, X. and Serra, A., “Improved Epoxy Thermosets by the Use of Poly(Ethyleneimine) Derivatives,” Physical Sciences Reviews, Vol. 2, No. 8, 2017.
[22] Zhang, D., Wang, R., Farhan, S., Jiang, H., Wang, N. and Yuan, L., “Curing Kinetics, Thermal and Mechanical Properties of TDE-85 Modified by Bicyclo-Benzoxazine,” RSC Advances, Vol. 6, No. 93, pp. 90994–91001, 2016.
[23] Gao, L., Zhang, Q., Li, H., Yu, S., Zhong, W., Sui, G. and Yang, X., “Effect of Epoxy Monomer Structure on the Curing Process and Thermo-Mechanical Characteristics of Tri-Functional Epoxy/Amine Systems: a Methodology Combining Atomistic Molecular Simulation with Experimental Analyses,” Polymer Chemistry, Vol. 8, No. 13, pp. 2016–2027, 2017.
[24] Bouanga, C.V., Couderc, H., Malucelli, G., Frechette, M.F., Camino, G., Savoie, S., Castellon, J. and Banet, L., “Dielectric study of a cyclo-aliphatic UV-curable epoxy resin copolymerized with a low glass transition co-monomer bearing methylene units,” Report Conference on Electrical Insulation and Dielectric Phenomena, pp. 655-659, 2011.
[25] Park, J.J., Kim, J.S., Yoon, C.Y., Shin, S.S., Lee, J.Y., Cheong, J.H., Kim, Y.W. and Kang, G.B., “Mechanical and electrical properties of cycloaliphatic epoxy/silica systems for electrical insulators for outdoor applications,” Transactions on Electrical and Electronic Materials, Vol. 16, No. 2, pp. 82-85, 2015.
[26] Laiwang, B., Liu, S.H., Tsai, Y.T., Deng, J., Jiang, H.C., Li, B. and Shu, C.M., “Effects of UV for cycloaliphatic epoxy resin via thermokinetic models, novel calorimetric technology, and thermogravimetric analysis,” Scientific Reports, Vol. 8, No. 1, pp. 15835-15843, 2018.
[27] Deng, J., Liu, X., Li, C., Jiang, Y., & Zhu, J.. “Synthesis and properties of a bio-based epoxy resin from 2,5-furandicarboxylic acid (FDCA)”. RSC Advances, Vol. 21, No. 5, 15930–39, 2015.
[28] Boussès, Y., Brulat-Bouchard, N., Bouchard, P.O., Abouelleil, H. and Tillier, Y., “Theoretical prediction of dental composites yield stress and flexural modulus based on filler volume ratio,” Dental Materials, Vol. 36, No. 1, pp. 97-107, 2020.
[29] Amini Majd, A., Mortezaei, M. and Amiri Amraei, I., “Curing behavior, Thermal, and Mechanical Properties of Epoxy/Polyamic Acid based on 4,4′‐Biphtalic Dianhydride and 3,3′‐Dihydroxybenzidine,” Polymer Engineering & Science, Vol. 60, No. 8, pp. 1917–1929, 2020.
[30] Nikzamir, M., Mortezaei, M. and Jahani, M., “Effect of Surface Area of Nanosilica Particles on the Cure Kinetics Parameters of an Epoxy Resin System,” Journal of Applied Polymer Science, Vol. 136, No. 37, 2019.
[31] Akherati, S. R., Mortezaei, M. and Amiri Amraei, I. “The Effect of Curing Temperature on Fracture Energy of Nanosilica Filled Epoxy with Different Particle Sizes,” In Persian, Journal of Science and Technology of Composites, Vol. 3, No. 4, pp. 389–396, 2017.
[32] Nikzamir M. and Mortezaei M., “Study of the Influence of Temperature and Nanosilica on Curing Behavior and Cure Kinetics Modelling of an Epoxy Resin System,” In Persian, Journal of Science and Technology of Composites, Vol. 3, No. 4, pp. 351–358, 2017.
[33] Ochiai, B. and Soegawa, K., “Glycidate as a High-Strength Epoxy Adhesive Curable with Amine under Ambient Conditions,” Polymers, Vol. 14, No. 5, p. 957, 2022.
[34] Karger‐Kocsis, J., Gryshchuk, O. and Jost, N., “Toughness Response of Vinylester/Epoxy‐Based Thermosets of Interpenetrating Network Structure as a Function of the Epoxy Resin Formulation: Effects of the Cyclohexylene Linkage,” Journal of Applied Polymer Science, Vol. 88, No. 8, pp. 2124–2131, 2003.
[35] Iyer, K. A., “Chain Mobility, Secondary Relaxation, and Oxygen Transport in Terephthalate Copolyesters with Rigid and Flexible Cyclic Diols,” Polymer, Vol. 129, pp. 117–126, 2017.
[36] Pirayesh, A., Qolizade, N., Talebi, S. and Salami-Kalajahi, M., “Application of Butane-1,4-Diyl Bis(2-Mercaptoacetate) as Dithiol Prepolymer for Preparation of Polythiourethane and Clay-based Nanocomposites,” Journal of Sulfur Chemistry, Vol. 43, No. 4, pp. 402–412, 2022.
[37] Zeng, C., Zhang, S., Ji, P., Qiu, Z., Li, Z., Wang, C. and Wang, H., “Facile Sustainable Synthesis of Polyester-Polycarbonate and Effects of the Carbonate on Thermal, Mechanical, and Transparency Properties,” ACS Sustainable Chemistry & Engineering, Vol. 11, No. 43, pp. 15754–15764, 2023.
[38] Li, Q., Ma, S., Wei, J., Wang, S., Xu, X., Huang, K., Wang, B., Yuan, W. and Zhu, J., “Preparation of Non-Planar-Ring Epoxy Thermosets Combining Ultra-Strong Shape Memory Effects and High Performance,” Macromolecular Research, Vol. 28, No. 5, pp. 480–493, 2020.