The Curing for Modified Vinyl Ester Resin by Hexamethylene Diisocyanate and Its Influence on Performances

Abstract

The commercial vinyl ester resins (VER) was modified by diphenylmethane diisocyanate (MDI) to enhance its toughness, which is called MVER. Hexamethylene diisocyanate (HDI), a common curing agent for polyurethane (PU), was found to be a reactive agent for MVER and can contribute to the toughness of MVER. Based on present experiment results, the crosslinking mechanism of MVER and HDI system is very similar to that of PU. The FTIR result shows the −NCO of HDI can react with the −OH of MVER. The microstructure of material prepared by MVER and HDI was characterized by NMR, and it was revealed that the unique microstructure leads to the good performances. The different content of HDI has an influence on the microstructure, and the microstructure gradually reduces the toughness and mechanical performances of the MVER cured with increasing concentration of reactive curing agent (HDI). This feature is consistent with a maximum in toughness as a function of the additive (HDI) content, followed by a rapid deterioration in toughness at higher concentrations. The toughness exhibits the maximum at such an HDI concentration (20wt%). Therefore, the special curing agent (HDI) and reactive mode is very important to the microstructure and mechanical properties of material. Furthermore, there should be other reactions which contribute to the curing and microstructure of the material, which needs the further research.

Keywords

modified vinyl ester / hexamethylene diisocyanate / mechanical properties / toughness

References

[1] Koh KT, Ryu GS, Lee JH. Effect of Curing Method on the Strength Development and Freezing-thawing Durability of the Concrete Incorporating High Volume Blast-furnace Slag Subjected to Initial Frost Damage[J]. Advanced Materials Research, 2013, 602–604: 962-967.

[2] Fakhari A, Rahmat AR, Wahit MU, et al. Mechanical Properties of Hybrid Thermosets from Vinyl Ester Resin and Acrylated Epoxidized Palm Oil (AEPO)[J]. Applied Mechanics and Materials, 2014, 695: 73-76.

[3] Cai X, Fu D, Qu A. Effects of Processing Conditions on the Properties of Epoxy Resin Microcapsule[J]. Journal of Wuhan University of Technology-Mater. Sci. Ed., 2015, 30(4): 689-694.

[4] Rogers DP. Lignin-derived Thermosetting Vinyl Ester Resins for High Performance Applications[J]. Dissertations & Theses — Gradworks, 2015

[5] Jiao W, Cai Y, Liu W, et al. Preparation of Carbon Fiber Unsaturated Sizing Agent for Enhancing Interfacial Strength of Carbon Fiber/Vinyl Ester Resin Composite[J]. Applied Surface Science, 2018, 439: 88-95.

[6] Chung IJ. The Cure Behavior of Rubber and Thermoplastic Elastomer Modified Vinyl Ester Resins[C]. In: APCChE 5th Congress, Kuala Lumpur, Malaysia, 1990

[7] Auad ML, Borrajo J, Aranguren MI. Morphology of Rubber-modified Vinyl Ester Resins Cured at Different Temperatures[J]. Journal of Applied Polymer Science, 2003, 89(1): 274-283.

[8] Auad ML, Proia M, Borrajo J, et al. Rubber Modified Vinyl Ester Resins of Different Molecular Weights[J]. Journal of Materials Science, 2002, 37(19): 4117-4126.

[9] Kunieda M, Takida H. Halogen-containing Thermoplastic Resin Composition[P]. US Patent 4,963,608. 1990-10-16

[10] López J, Rico M, Ramírez C, et al. Epoxy Resin Modified with a Thermoplastic[J]. Journal of Thermal Analysis and Calorimetry, 2010, 99(1): 75-81.

[11] Jackson RJ. Thickenable Thermosetting Vinyl Ester Resins[P]. US Patent 4, 197, 390. 1980-4-8

[12] Gupta N, Ye R, Porfiri M. Comparison of Tensile and Compressive Characteristics of Vinyl Ester/Glass Microballoon Syntactic Foams[J]. Composites Part B: Engineering, 2010, 41(3): 236-245.

[13] Rolls JA, Brenis KL. High Bulk Density Rigid Poly (Vinyl Chloride) Resin Powder Composition and Preparation Thereof[P]. US Patent 4, 239, 679. 1980-12-16

[14] Ku H. Curing Vinyl Ester Particle-reinforced Composites Using Microwaves[J]. Journal of Composite Materials, 2003, 37(22): 2027-2042.

[15] Gryshchuk O, Jost N, Karger-Kocsis J. Toughening of Vinylester-urethane Hybrid Resins through Functionalized Polymers[J]. Journal of Applied Polymer Science, 2002, 84(3): 672-680.

[16] Lorah DP. Grafted Core-shell Polymer Compositions Using Polyfunctional Compounds[P]. US Patent 4, 876, 313. 1989-10-24

[17] Shiratsuchi K, Hokazono H. Aqueous Dispersion of Core/Shell-type Composite Particles with Colloidal Silica as the Cores and with Organic Polymer as the Shells and Production Method Thereof[P]. US Patent 5, 856, 379. 1999-1-5

[18] Chacko VP, Kraft TJ. Glass Reinforced Polyamide Composition Containing Acrylic Core/Shell Polymer[P]. US Patent 4, 495, 324. 1985-1-22

[19] Nair CPR. Advances in Addition-cure Phenolic Resins[J]. Progress in Polymer Science, 2004, 29(5): 401-498.

[20] Lu Y, Larock RC. Novel Polymeric Materials from Vegetable Oils and Vinyl Monomers: Preparation, Properties, and Applications[J]. Chem. Sus.Chem., 2009, 2(2): 136-147.

[21] Alexander IJ. Elastomer Modified Unsaturated Polymers[P]. US Patent 4,530,962. 1985-7-23

[22] Ramalingam PS, Mayandi K, Srinivasan T, et al. A Study on E-glass Fiber Reinforced Interpenetrating Polymer Network (Vinyl Ester/polyurethane) Laminate’s Flexural Analysis[J]. Materials Today: Proceedings, 2020, 33(1): 854-858.