Abstract
In this study, a new hybrid alkyd resin was formulated using melamine-based hyperbranched polymer having 24 hydroxyl groups on its structure and relatively low molecular weight alkyd. The alkyd was synthesized using an oil mixture (40% linseed + 60% sunflower). Melamine was used as the core molecule for the hyperbranched polymer due to its excellent properties such as greater hardness, alkali and solvent resistance, and thermal stability. Melamine was first hydroxylated using formaldehyde and changed into hexamethylol melamine. This product was then twice hydroxylated with dimethylol propionic acid to obtain a hyperbranched polymer with 24 hydroxyl end groups. It was then reacted with low molecular weight alkyd resin at different proportions. The product had a low viscosity and could easily flow like oil. It is a solvent-free and water-free liquid. The ‘hyperbranched polymer/alkyd’ ratio affected physical properties of the liquid polymer and also the mechanical properties of the hardened polymer, which can be used for surface coating. The viscosity of the liquid resin decreases from 148 to 8.84 Pa.s as the hyperbranched-polymer-to-alkyd ratio is decreased from 1:3 to 1:24. On the other hand, the hardness of heat-treated resin decreases from 198 Persoz to 43 Persoz, respectively. That is, the increase in the amount of hyperbranched polymer in the resin increases hardness, whereas the increase in the amount of alkyd decreases it. The mechanical tests of hardened resins showed that all specimens passed conical mandrel bending test, and they all depicted high adhesion, and high abrasion and impact resistance. The specimens also had excellent gloss properties.
Similar content being viewed by others
References
Lindeboom, J, “Air-Drying High Solids Alkyd Pants for Decorative Coatings.” Prog. Org. Coat., 34 (1–4) 147–151 (1997)
Manczyk, K, Szewczyk, P, “Highly Branched High Solids Alkyd Resins.” Prog. Org. Coat., 44 (2) 99–109 (2002)
Malmström, E, Johansson, M, Hult, A, “Hyperbranched Aliphatic Polyesters.” Macromolecules, 28 (5) 1698–1703 (1995)
van Benthem, RATM, “Novel Hyperbranched Resins for Coating Applications.” Prog. Org. Coat., 40 (1–4) 203–214 (2000)
Flory, PJ, Principles of Polymer Chemistry. Cornell University Press, New York (1953)
Bao, C-L, Wang, L-S, Zhang, A-Q, “Synthesis and Properties of Waterborne Hyperbranched Aliphatic Polyester Clear Coats.” J. Taiwan Inst. Chem. Eng., 40 (2) 174–179 (2009)
Gao, C, Yan, D, “Hyperbranched Polymers: From Synthesis to Applications.” Prog. Polym. Sci., 29 (3) 183–275 (2004)
Kricheldorf, HR, “Hyperbranched Cyclic and Multicyclic Polymers by ‘a2 + b4’ Polycondensations.” J. Polym. Sci. Part A Polym. Chem., 47 (8) 1971–1987 (2009)
Seiler, M, “Hyperbranched Polymers: Phase Behavior and New Applications in the Field of Chemical Engineering.” Fluid Phase Equilib., 241 (1–2) 155–174 (2006)
Yates, CR, Hayes, W, “Synthesis and Applications of Hyperbranched Polymers.” Eur. Polym. J., 40 (7) 1257–1281 (2004)
Bat, E, Gündüz, G, Kisakürek, D, Akhmedov, IM, “Synthesis and Characterization of Hyperbranched and Air Drying Fatty acid Based Resins.” Prog. Org. Coat., 55 (4) 330–336 (2006)
Karakaya, C, Gündüz, G, Aras, L, Mecidoglu, IA, “Synthesis of Oil Based Hyperbranched Resins and Their Modification with Melamine-Formaldehyde Resin.” Prog. Org. Coat., 59 (4) 265–273 (2007)
Li, T, Qin, H, Liu, Y, Zhong, X, Yu, Y, Serra, A, “Hyperbranched Polyester as Additives in Filled and Unfilled Epoxy-Novolac Systems.” Polymer, 53 (25) 5864–5872 (2012)
Twibanire, JdA, Grindley, TB, “Polyester Dendrimers.” Polymers, 4 (1) 794 (2012)
Segawa, Y, Higashihara, T, Ueda, M, “Synthesis of Hyperbranched Polymers with Controlled Structure.” Polym. Chem., 4 (6) 1746–1759 (2013)
Zhang, T, Howell, BA, Dumitrascu, A, Martin, SJ, Smith, PB, “Synthesis and Characterization of Glycerol-Adipic Acid Hyperbranched Polyesters.” Polymer, 55 (20) 5065–5072 (2014)
Tuerp, D, Bruchmann, B, “Dendritic Polyurea Polymers.” Macromol. Rapid Commun., 36 (2) 138–150 (2015)
Konwar, U, Karak, N, “Mesua ferrea L. Seed Oil-Based Highly Branched Polyester Resins.” Polym. Plast. Technol. Eng., 48 (9) 970–975 (2009)
Parzuchowski, PG, Grabowska, M, Jaroch, M, Kusznerczuk, M, “Synthesis and Characterization of Hyperbranched Polyesters from Glycerol-Based AB2 Monomer.” J. Polym. Sci., Part A: Polym. Chem., 47 (15) 3860–3868 (2009)
Murillo, EA, Vallejo, PP, López, BL, “Effect of Tall Oil Fatty Acids Content on the Properties of Novel hyperbranched Alkyd Resins.” J. Appl. Polym. Sci., 120 (6) 3151–3158 (2011)
Zhang, L-Y, Jiao, Q-Z, Zhao, Y, Zhou, M-J, Feng, W, Ge, Y-R, “Synthesis and Properties of UV-Curable Hyperbranched Polyester.” Acta Chim. Sin., 69 (17) 2031–2038 (2011)
Singh, AP, Suryanarayana, C, Baloji Naik, R, Gunasekaran, G, “Development of Hyperbranched Polyester Polyol-Based Waterborne Anticorrosive Coating.” J. Coat. Technol. Res., 13 (1) 41–51 (2016)
Huang, S, Xiao, J, Zhu, Y, Qu, J, “Synthesis and Properties of Multiarm Star Hydroxyl-Terminated Polyesters for Two-Component Polyurethane Coatings.” J. Coat. Technol. Res., 14 (3) 505–516 (2017)
Sharmin, E, Zafar, F, Akram, D, Alam, M, Ahmad, S, “Recent Advances in Vegetable Oils Based Environment Friendly Coatings: A Review.” Ind. Crops Prod., 76 (Supplement C) 215–229 (2015)
Johansson, K, Bergman, T, Johansson, M, “Hyperbranched Aliphatic Polyesters and Reactive Diluents in Thermally Cured Coil Coatings.” ACS Appl. Mater. Interfaces, 1 (1) 211–217 (2009)
Zhang, X, “Modifications and Applications of Hyperbranched Aliphatic Polyesters Based on Dimethylolpropionic Acid.” Polym. Int., 60 (2) 153–166 (2011)
Malmström, E, Hult, A, “Hyperbranched Polymers.” J. Macromol. Sci. Part C, 37 (3) 555–579 (1997)
Voit, B, “New Developments in Hyperbranched Polymers.” J. Polym. Sci. Part A Polym. Chem., 38 (14) 2505–2525 (2000)
Johansson, M, Glauser, T, Jansson, A, Hult, A, Malmström, E, Claesson, H, “Design of Coating Resins by Changing the Macromolecular Architecture: Solid and Liquid Coating Systems.” Prog. Org. Coat., 48 (2) 194–200 (2003)
Güç, E, Gündüz, G, Gündüz, U, “Fatty Acid Based Hyperbranched Polymeric Nanoparticles for Hydrophobic Drug Delivery.” Drug Dev. Ind. Pharm., 36 (10) 1139–1148 (2010)
Haseebuddin, S, Parmar, R, Waghoo, G, Ghosh, SK, “Study of Hexafunctional Polyol in High Solids Air-Drying Alkyd: Improved Film Performance.” Prog. Org. Coat., 64 (4) 446–453 (2009)
Mejía, MC, Murillo, EA, “Polyfunctional Macromonomers Obtained from 2,2-Bis(hydroxymethyl) Propanoic Acid and Tall Oil Fatty Acids.” J. Appl. Polym. Sci. 132(23) 42029 (2015). https://doi.org/10.1002/app.42029
Radičević, R, Jovičić, M, Budinski-Simendić, J, “Preparation and Curing of Alkyd Based on Ricinoleic Acid/Melamine Coatings.” Prog. Org. Coat., 71 (3) 256–264 (2011)
Ikladious, NE, Mansour, SH, Asaad, JN, Emira, HS, Hilt, M, “Synthesis and Evaluation of New Hyperbranched Alkyds for Coatings.” Prog. Org. Coat., 89 (Supplement C) 252–259 (2015)
Selim, MS, Shenashen, MA, Elmarakbi, A, El-Saeed, A, Selim, MM, El-Safty, SA, “Sunflower Oil-Based Hyperbranched Alkyd/Spherical ZnO Nanocomposite Modeling for Mechanical and Anticorrosive Applications.” RSC Adv., 7 (35) 21796–21808 (2017)
Naik, RB, Ratna, D, Singh, SK, “Synthesis and Characterization of Novel Hyperbranched Alkyd and Isocyanate Trimer Based High Solid Polyurethane Coatings.” Prog. Org. Coat., 77 (2) 369–379 (2014)
Salleh, MZ, Badri, K, Ahmd, SH, Mahmood, MH, “Properties of Radiation Curable Hyperbranched Polyurethane Acrylate from Palm Oil Oleic Acid.” Nucl. Sci. Tech., 24 (S1) S010303-1–S010303–6 (2013)
Rozman, HD, Tai, NL, Sua, PR, Azniwati, AA, Tay, GS, “Preparation and Characterization of Ultraviolet (UV) Radiation Curable Resin from Palm Oil.” J. Coat. Technol. Res., 13 (6) 1009–1019 (2016)
Mirshahi, F, Bastani, S, Ganjaee Sari, M, “Studying the Effect of Hyperbranched Polymer Modification on the Kinetics of Curing Reactions and Physical/Mechanical Properties of UV-Curable Coatings.” Prog. Org. Coat., 90 (Supplement C) 187–199 (2016)
Yari, H, Mohseni, M, Ranjbar, Z, Messori, M, Naimi-Jamal, MR, “Novel Toughened Automotive Clearcoats Modified by a Polyester-Amide Hyperbranched Polymer: Structural and Mechanical Aspects.” Polym. Adv. Technol., 24 (5) 495–502 (2013)
Pan, X, Webster, DC, “Impact of Structure and Functionality of Core Polyol in Highly Functional Biobased Epoxy Resins.” Macromol. Rapid Commun., 32 (17) 1324–1330 (2011)
Konwar, U, Karak, N, Jana, T, “Vegetable Oil-Based Highly Branched Polyester Modified Epoxy Based Low VOC High Solid Industrial Paint.” J. Appl. Polym. Sci., 125 (S2) E2–E9 (2012)
Foix, D, Rodríguez, MT, Ferrando, F, Ramis, X, Serra, A, “Combined Use of Sepiolite and a Hyperbranched Polyester in the Modification of Epoxy/Anhydride Coatings: A Study of the Curing Process and the Final Properties.” Prog. Org. Coat., 75 (4) 364–372 (2012)
Bruchmann, B, “Dendritic Polymers Based on Urethane Chemistry—Syntheses and Applications.” Macromol. Mater. Eng., 292 (9) 981–992 (2007)
Priyanka, KG, Mishra, AK, Kantheti, S, Narayan, R, Raju, KVSN, “Synthesis of Triazole Ring-Containing Pentol Chain Extender and Its Effect on the Properties of Hyperbranched Polyurethane-Urea Coatings.” J. Appl. Polym. Sci., 126 (6) 2024–2034 (2012)
Kyritsis, A, Raftopoulos, K, Rehim, MA, Shabaan, SS, Ghoneim, A, Turky, G, “Structure and Molecular Dynamics of Hyperbranched Polymeric Systems with Urethane and Urea Linkages.” Polymer, 50 (16) 4039–4047 (2009)
Mishra, AK, Narayan, R, Raju, KVSN, Aminabhavi, TM, “Hyperbranched Polyurethane (HBPU)-Urea and HBPU-Imide Coatings: Effect of Chain Extender and NCO/OH Ratio on Their Properties.” Prog. Org. Coat., 74 (1) 134–141 (2012)
Jena, KK, Chattopadhyay, DK, Raju, KVSN, “Synthesis and Characterization of Hyperbranched Polyurethane–Urea Coatings.” Eur. Polym. J., 43 (5) 1825–1837 (2007)
Kumari, S, Mishra, AK, Chattopadhyay, DK, Raju, KVSN, “Synthesis and Characterization of Hyperbranched Polyesters and Polyurethane Coatings.” J. Polym. Sci. Part A Polym. Chem., 45 (13) 2673–2688 (2007)
Mishra, AK, Allauddin, S, Radhika, KR, Narayan, R, Raju, KVSN, “Effect of NCO/OH Ratio and Ce–Zr Nanoparticles on the Thermo-Mechanical Properties of Hyperbranched Polyurethane Urea Coatings.” Polym. Adv. Technol., 22 (6) 882–890 (2011)
Mishra, AK, Narayan, R, Raju, KVSN, “Structure–Property Correlation Study of Hyperbranched Polyurethane–Urea (HBPU) Coatings.” Prog. Org. Coat., 74 (3) 491–501 (2012)
Deka, H, Karak, N, “Bio-Based Hyperbranched Polyurethanes for Surface Coating Applications.” Prog. Org. Coat., 66 (3) 192–198 (2009)
Kumari, S, Mishra, AK, Krishna, AVR, Raju, KVSN, “Organically Modified Montmorillonite Hyperbranched Polyurethane–Urea Hybrid Composites.” Prog. Org. Coat., 60 (1) 54–62 (2007)
Wan, D, Li, Z, Huang, J, “Synthesis of a New Type of Core–Shell Particle from Hyperbranched Polyglycerol.” J. Polym. Sci. Part A: Polym. Chem., 43 (22) 5458–5464 (2005)
Asif, A, Shi, W, “UV Curable Waterborne Polyurethane Acrylate Dispersions Based on Hyperbranched Aliphatic Polyester: Effect of Molecular Structure on Physical and Thermal Properties.” Polym. Adv. Technol., 15 (11) 669–675 (2004)
Samuelsson, J, Sundell, P-E, Johansson, M, “Synthesis and Polymerization of a Radiation Curable Hyperbranched Resin Based on Epoxy Functional Fatty Acids.” Prog. Org. Coat., 50 (3) 193–198 (2004)
Tasic, S, Bozic, B, Dunjic, B, “Synthesis of New Hyperbranched Urethane-Acrylates and Their Evaluation in UV-Curable Coatings.” Prog. Org. Coat., 51 (4) 320–327 (2004)
Dzunuzovic, E, Tasic, S, Bozic, B, Babic, D, Dunjic, B, “UV-Curable Hyperbranched Urethane Acrylate Oligomers Containing Soybean Fatty acids.” Prog. Org. Coat., 52 (2) 136–143 (2005)
Lu, WH, Xu, WJ, Wu, YM, Zhou, X, Lu, YB, Xiong, YQ, “Synthesis of Dendritic Poly(urethane acrylate) Used for UV-Curable Coatings.” Prog. Org. Coat., 56 (2) 252–255 (2006)
Sun, F, Shi, J, Du, H-g, Nie, J, “Synthesis and Characterization of Hyperbranched Photosensitive Polysiloxane Urethane Acrylate.” Prog. Org. Coat., 66 (4) 412–419 (2009)
Džunuzović, ES, Tasić, SV, Božić, BR, Džunuzović, JV, Dunjić, BM, Jeremić, KB, “Mechanical and Thermal Properties of UV Cured Mixtures of Linear and Hyperbranched Urethane Acrylates.” Prog. Org. Coat., 74 (1) 158–164 (2012)
Mishra, RS, Mishra, AK, Raju, KVSN, “Synthesis and Property Study of UV-Curable Hyperbranched Polyurethane Acrylate/ZnO Hybrid Coatings.” Eur. Polym. J., 45 (3) 960–966 (2009)
Gao, Q, Li, H, Zeng, X, “Preparation and Characterization of UV-Curable Hyperbranched Polyurethane Acrylate.” J. Coat. Technol. Res., 8 (1) 61–66 (2011)
Şabani, S, Önen, AH, Güngör, A, “Preparation of Hyperbranched Polyester Polyol-Based Urethane Acrylates and Applications on UV-Curable Wood Coatings.” J. Coat. Technol. Res., 9 (6) 703–716 (2012)
Lin, J, Zeng, X, Hou, Y, Shi, H, Lin, J, “Synthesis and Characterization of UV-curable Hyperbranched Urethane Acrylate.” Polym. Plast. Technol. Eng., 47 (3) 237–241 (2008)
Bao, F, Shi, W, “Synthesis and Properties of Hyperbranched Polyurethane Acrylate Used for UV Curing Coatings.” Prog. Org. Coat., 68 (4) 334–339 (2010)
Miao, H, Cheng, L, Shi, W, “Fluorinated Hyperbranched Polyester Acrylate Used as an Additive for UV Curing Coatings.” Prog. Org. Coat., 65 (1) 71–76 (2009)
Liu, P, Gu, A, Liang, G, Guan, Q, Yuan, L, “Preparation and Properties of Novel High Performance UV-Curable Epoxy Acrylate/Hyperbranched Polysiloxane Coatings.” Prog. Org. Coat., 74 (1) 142–150 (2012)
Zhang, Y, Asif, A, Shi, W, “Highly Branched Polyurethane Acrylates and Their Waterborne UV Curing Coating.” Prog. Org. Coat., 71 (3) 295–301 (2011)
Ortiz, RA, Flores, RVG, García Valdéz, AE, Duarte, MLB, “Novel Second Generation Dendrimer with Terminal Thiol Groups and its Thiol–Ene Photopolymerization with Unsaturated Monomers.” Prog. Org. Coat., 69 (4) 463–469 (2010)
Trey, SM, Nilsson, C, Malmström, E, Johansson, M, “Thiol–Ene Networks and Reactive Surfaces Via Photoinduced Polymerization of Allyl Ether Functional Hyperbranched Polymers.” Prog. Org. Coat., 67 (3) 348–355 (2010)
Han, W, Lin, B, Zhou, Y, Song, J, “Synthesis and Properties of UV-Curable Hyperbranched Polyurethane Acrylate Oligomers Containing Photoinitiator.” Polym. Bull., 68 (3) 729–743 (2012)
Dixon, JK, Woodberry, NT, Costa, GW, “The Dissociation Constants of Melamine and Certain of Its Compounds.” J. Am. Chem. Soc., 69 (3) 599–603 (1947)
Palanikkumaran, M, Gupta, KK, Agrawal, AK, Jassal, M, “Highly Stable Hexamethylolmelamine Microcapsules Containing n-Octadecane Prepared by In Situ Encapsulation.” J. Appl. Polym. Sci., 114 (5) 2997–3002 (2009)
Konar, BB, “A Kinetic and Rheometric Investigation of Hexamethylol Melamine Derivative on the Cure of Natural Rubber Compounds.” J. Appl. Polym. Sci., 63 (2) 233–237 (1997)
Manley, TR, “Thermal Stability of Hexamethylolmelamine.” Polym. J., 4 (1) 111–113 (1972)
Aydin, S, Akçay, H, Özkan, E, Güner, FS, Erciyes, AT, “The Effects of Anhydride Type and Amount on Viscosity and Film Properties of Alkyd Resin.” Prog. Org. Coat., 51 (4) 273–279 (2004)
Gündüz, G, Chemistry, Materials, and Properties of Surface Coatings: Traditional and Evolving Technologies. DEStech Publications Inc, Lancaster (2015)
Sailer, RA, Wegner, JR, Hurtt, GJ, Janson, JE, Soucek, MD, “Linseed and Sunflower Oil Alkyd Ceramers.” Prog. Org. Coat., 33 (2) 117–125 (1998)
Schweitzer, PA, Paint and Coatings: Applications and Corrosion Resistance. CRC, New York (2006)
Acknowledgments
This research was supported by TÜBİTAK (Turkish Scientific and Technical Research Council), Project No. 108M204.
Author information
Authors and Affiliations
Corresponding author
Rights and permissions
About this article
Cite this article
Gündüz, G., Keskin, N., Çolak, Ü. et al. Synthesis and characterization of solvent-free hybrid alkyd resin with hyperbranched melamine core. J Coat Technol Res 15, 831–843 (2018). https://doi.org/10.1007/s11998-017-0031-6
Published:
Issue Date:
DOI: https://doi.org/10.1007/s11998-017-0031-6