Cemil DIZMAN, Elif CERRAHOĞLU KAÇAKGİL, Levent BABAYİĞİT, Caner ARAR

Preparation and Characterization of Polyaspartic and a High Solids Acrylic Copolymer Polyol Based Polyurethanes

In this work, a high solids acrylic copolymer polyol (poly(MMA/BA/HEMA/AA)) was synthesized from the polymerization of methyl methacrylate (MMA), butyl acrylate (BA), hydroxyethyl methacrylate (HEMA) and acrylic acid (AA) and was added to the polyaspartic resin. The polyaspartic-polyol mixtures reacted with polyisocyanates to create hybrid polyurethane-polyaspartic hybrid coatings. Different amounts of synthesized acrylic copolymer (5, 10, and 20% of total resin mixture) were mixed into polyaspartic resin and subsequently reacted with polyisocyanates in a 1:1 molar ratio. The characterization of the polymer was performed with Gel Permeation Chromatography (GPC), Fourier-Transform Infrared-Attenuated Total Reflection (FTIR-ATR) and Differential Scanning Calorimetry (DSC). The determination of physical and mechanical properties of the hybrid coatings was accomplished by hardness, glossiness, abrasion, stress-strain, corrosion, and impact tests. The results indicated that by adding high solids acrylic copolymer (HSAC), the drawbacks of polyaspartic resin (short pot life, hardness and brittleness, and poor adhesiveness) have been largely eliminated without reducing its intrinsic properties. The pot life increased from 16 minutes to 27 minutes and shore D hardness decreased from 60-65 to 52-55 as the polyol content increased in the mixtures. The acrylic polyols and aspartic mixtures may be used in the preparation of paints and varnishes applied on concrete, metal, and wood surfaces.

Keywords:

Acrylic copolymer coating, high solids acrylic polyols, paint, polyaspartic,

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1. Shojaei B, Najafi M, Yazdanbakhsh A, Abtahi M, Zhang C. A review on the applications of polyurea in the construction industry. Polym Adv Technol [Internet]. 2021 Aug 1 [cited 2023 Jun 12];32(8):2797–812.
2. Szafran J, Matusiak A. LIGHTWEIGHT STRUCTURES in CIVIL ENGINEERING POLYUREA COATING SYSTEMS: DEFINITION, RESEARCH, APPLICATIONS. 2016;
3. Iqbal N, Tripathi M, Parthasarathy S, Kumar D, Roy PK. Polyurea spray coatings: Tailoring material properties through chemical crosslinking. Prog Org Coat. 2018 Oct 1;123:201–8.
4. T A, M A, Jayaprabakar J, Jeevahan J, Rb D. Study on mechanical properties of polyurea coating with various process parameters. [Internet]. 2020 [cited 2023 Jun 12];25(5):257–63.
5. Sánchez-Ferrer A, Soprunyuk V, Engelhardt M, Stehle R, Gilg HA, Schranz W, et al. Polyurea Networks from Moisture-Cure, Reaction-Setting, Aliphatic Polyisocyanates with Tunable Mechanical and Thermal Properties. ACS Appl Polym Mater [Internet]. 2021 Aug 13 [cited 2023 Jun 12];3(8):4070–8.
6. Editors A, Bhudolia SK, Chandrakant Joshi S, Leong Sing S, Min Huang W, Luo J, et al. Mini-Review of Self-Healing Mechanism and Formulation Optimization of Polyurea Coating. Polymers 2022, Vol 14, Page 2808 [Internet]. 2022 Jul 9 [cited 2023 Jun 12];14(14):2808.
7. Sánchez-Ferrer A, Rogez D, Martinoty P. Synthesis and Characterization of New Polyurea Elastomers by Sol/Gel Chemistry. Macromol Chem Phys [Internet]. 2010 Aug 2 [cited 2023 Jun 12];211(15):1712–21.
8. Santana JS, Cardoso ES, Triboni ER, Politi MJ. Polyureas Versatile Polymers for New Academic and Technological Applications. Polymers 2021, Vol 13, Page 4393 [Internet]. 2021 Dec 15 [cited 2023 Jun 12];13(24):4393.
9. Liu XP, Zheng TL. The Synthesis of a Polyaspartic Acid Ester and Development of the Coatings. Adv Mat Res [Internet]. 2014 [cited 2023 Jun 12];842:297–301.
10. Effect of Temperature on Tensile Curve of Polyaspartic Ester Polyurea and Its Activation Energy Analysis - IOPscience [Internet]. [cited 2023 Jun 12].
11. Bringing Polyaspartic Technology to the Next Level: Low Viscous Solvent-free Floor Coatings. ENVVT 2014 / / Karl H. - PDF Free Download [Internet]. [cited 2023 Jun 12].
12. Feng J, Liao LM, Chen L, Xiao CJ, Wang SF, Li H. Research on the Formula of Polyaspartic Ester Polyurea Concrete Coating and its Application. Applied Mechanics and Materials [Internet]. 2013 [cited 2023 Jun 12];423–426:1159–63.
13. Jing F, Wei H, Zhen L, Zai-Qin W. Aliphatic Polyurea Coating Materials Based on Novel Polyaspartic Ester： Preparation and Application. Journal of Yangtze River Scientific Research Institute [Internet]. 2012 Feb 1 [cited 2023 Jun 12];29(2):64.
14. Lu P, Huang WB, Ma XQ, Liu XD. Novel Polyaspartic Ester Polyureas Based on Flexible Polyaspartic Ester. Adv Mat Res [Internet]. 2011 [cited 2023 Jun 12];197–198:1294–8.
15. Carl Angeloff PE, Edward P. Squiller PhD, and Kurt E. Best, Bayer Corporation. Two-Component Aliphatic Polyurea Coatings for High Productivity Applications [Internet]. [cited 2023 Jun 12].
16. Ii DJP. Polyurea Elastomer Technology: History, Chemistry & Basic Formulating Techniques.
17. Dudley J. Primeaux II. Polyurea vs Polyurethane & Polyurethane/Polyurea: What’s the Difference? [Internet]. [cited 2023 Jun 12].
18. Golling FE, Pires R, Hecking A, Weikard J, Richter F, Danielmeier K, et al. Polyurethanes for coatings and adhesives – chemistry and applications. Polym Int [Internet]. 2019 May 1 [cited 2023 Jun 12];68(5):848–55.
19. Smith1 A, Eng2 B. INTERCORR2010_365 Polyaspartic Coatings That Perform as Well as Polyurethane Coatings. 2010;
20. Carl Angeloff PE, Edward P. Squiller PhD, and Kurt E. Best, Bayer Corporation. Two-Component Aliphatic Polyurea Coatings for High Productivity Applications [Internet]. [cited 2023 Jun 12].
21. Assarian A, Martinez S. Improving Polyaspartic Anti-Corrosion Coating Protective Properties with the use of Nano-silica. Acta Chim Slov [Internet]. 2018 Sep 17 [cited 2023 Jun 12];65(3):569–77.
22. Eco-Friendly Hyperbranched Polyaspartic Polyol and Polyurethane-Urea-Polyurea Hybrid Coatings | 2021-02-11 | PCI Magazine [Internet]. [cited 2023 Jun 12].
23. Petit H, Henry N, Krebs A, Uytterhoeven G, Jong F de. Ambient cure high solids acrylic resins for automotive refinish clear coat applications. Prog Org Coat. 2001 Nov 1;43(1–3):41–9.
24. Ding K, Liu J, Chen H, Wang H. Hyper-branched acrylic resin with high solid contents. [Internet]. 2017 Oct 23 [cited 2023 Jun 12];31(9):1149–60.
25. Diakournakos CD, Xu Q, Jones FN, Baghdachi J, Wu L. Synthesis of acrylic resins for high-solids coatings by solution and separation polymerization. Journal of Coatings Technology [Internet]. 2000 [cited 2023 Jun 12];72(908):61–70. 17. Ii DJP. Polyurea Coatings: That Was Then, This is Now. 2004;
26. Kim JW, Lee DC, Choi JS. Synthesis of Eco-Friendly High Solid Acrylic Resins and Curing Properties of Acrylic Urethane Resin Coatings. Korean Chemical Engineering Research [Internet]. 2017 Oct 1 [cited 2023 Jun 12];55(5):586–92.
27. Wendels S, Avérous L. Biobased polyurethanes for biomedical applications. Bioact Mater. 2021 Apr 1;6(4):1083–106.
28. Akay O, Altinkok C, Acik G, Yuce H, Ege GK. A bio-based and non-toxic polyurethane film derived from Luffa cylindrica cellulose and ʟ-Lysine diisocyanate ethyl ester. Eur Polym J. 2021 Dec 5;161:110856.
29. Taheri M, Jahanfar M, Ogino K. Synthesis of acrylic resins for high-solids traffic marking paint by solution polymerization. [Internet]. 2019 Jan 1 [cited 2023 Jun 12];22(1):213–25.
30. Zheng J, Aziz T, Fan H, Haq F, Ullah Khan F, Ullah R, et al. Synergistic impact of cellulose nanocrystals with multiple resins on thermal and mechanical behavior. Zeitschrift fur Physikalische Chemie [Internet]. 2021 Oct 1 [cited 2023 Jun 12];235(10):1247–62.
31. Ulianas A, Heng LY, Ahmad M. A Biosensor for Urea from Succinimide-Modified Acrylic Microspheres Based on Reflectance Transduction. Sensors 2011, Vol 11, Pages 8323-8338 [Internet]. 2011 Aug 26 [cited 2023 Jun 12];11(9):8323–38.
32. Lastovickova DN, Toulan FR, Mitchell JR, VanOosten D, Clay AM, Stanzione JF, et al. Resin, cure, and polymer properties of photopolymerizable resins containing bio-derived isosorbide. J Appl Polym Sci [Internet]. 2021 Jul 5 [cited 2023 Jun 12];138(25):app50574.
33. Zhang Y, Wang H, Eberhardt TL, Gu Q, Pan H. Preparation of carboxylated lignin-based epoxy resin with excellent mechanical properties. Eur Polym J. 2021 May 5;150:110389.
34. Çöpoğlu N, Çiçek B. Abrasion resistant glass-ceramic coatings reinforced with WC-nanoparticles. Surf Coat Technol. 2021 Aug 15;419:127275.
35 . Calabrese L, Proverbio E, Di Bella G, Galtieri G, Borsellino C. Failure behaviour of SPR joints after salt spray test. Eng Struct. 2015 Jan 1;82:33–43.
36. Fujita S, Mizuno D. Corrosion and corrosion test methods of zinc coated steel sheets on automobiles. Corros Sci. 2007 Jan 1;49(1):211–9.