Abstract
A series of ambient-temperature self-crosslinked waterborne polyurethanes denoted as WBPUs were successfully synthesized by incorporating a novel diol chain extender bearing two ketone groups, 2,2-bis(4-(2-hydroxypropoxy levulinate)phenyl)-propane (BHLPP), which was prepared using 2,2-bis(4-(2,3-epoxypropoxy)phenyl)-propane and levulinic acid, with 4,4-methylenedicyclohexyl diisocyanate, poly-neopentylene adipate glycol, and dimethylolpropionic acid. After post-adding adipic dihydrazide (ADH), self-crosslinking was achieved by the reaction between the ketone (–CO–) of BHLPP and the hydrazine (–NHNH2) of ADH during film formation. For comparison, noncrosslinked waterborne polyurethane (WPU) without BHLPP and ADH was prepared. The structure of BHLPP was characterized by IR and NMR. The properties of the WPU and WBPU dispersions were investigated by measuring the stability, particle size, and morphology. The effects of the ratio of n(–NHNH2)/n(–CO–) and the content of BHLPP were studied in terms of hardness, water resistance, solvent resistance, and thermal properties of WPU and WBPU films. The WBPU dispersions exhibited excellent stability, bimodal distribution, and regular spheroid morphology. The optimal ratio of n(–NHNH2)/n(–CO–) for ketone–hydrazine self-crosslinking was 0.75:1. Importantly, the WBPU films showed superior hardness, water resistance, solvent resistance, and thermal properties to WPU film.
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References
Coogan, RG, “Post-Crosslinking of Water-Borne Urethanes.” Prog. Org. Coat., 32 51–63 (1997)
Tillet, G, Boutevin, B, Ameduri, B, “Chemical Reactions of Polymer Crosslinking and Post-Crosslinking at Room and Medium Temperature.” Prog. Polym. Sci., 36 191–217 (2011)
Overbeek, GC, “Polyurethane Coating Composition.” US Patent 4,983,662, 1991
Lai, JZ, Ling, HJ, Yeh, JT, Chen, KN, “New Self-Curable, Aqueous-Based Polyurethane System by an Isophorone Diisocyanate/Uretedione Aziridinyl Derivative Process.” J. Appl. Polym. Sci., 94 845–859 (2004)
Qiu, YP, Tang, LM, “Ambient Curable Waterborne Polyurethane Coating Based on the Reaction between Carboxyl and Aziridinyl Groups.” J. Tsinghua Univ., 48 110–113 (2008)
Liu, YH, Zhang, QS, “Synthesis, Characterization and Application of Waterborne Polyurethane Crosslinker.” Petrochem. Technol., 40 901–906 (2011)
Li, XJ, Hu, J, Sun, DX, Zhang, YH, “Synthesis and Properties of Intermolecular Self-Crosslinking Organic-Inorganic Hybrid Waterborne Polyurethane Based on CuAAC Reaction.” Chem. J. Chinese. U., 34 2871–2879 (2013)
Chen, GN, Chen, KN, “Self-Curing Behaviors of Single Pack Aqueous-Based Polyurethane System.” J. Appl. Polym. Sci., 63 1609–1623 (1997)
Lai, JZ, Chen, PJ, Yeh, JT, Chen, KN, “A Cross Self-Curing System for an Aqueous-Based PU Hybrid.” J. Appl. Polym. Sci., 97 550–558 (2005)
Pham, HH, Winnik, MA, “Polymer Interdiffusion vs Cross-Linking in Carboxylic Acid-Carbodiimide Latex Films. Effect of Annealing Temperature, Reactive Group Concentration, and Carbodiimide Substituent.” Macromolecules, 39 1425–1435 (2006)
Lum, D, Suffern, NY, Patel, P, Viejo, A, Calif, “Water-Based, Storage, Self-Curing Coating Composition.” US Patent 5,916,960, 1999
Huang, LL, Lee, PC, Chen, LW, Hsieh, KH, “Comparison of Epoxides on Grafting Collagen to Polyurethane and Their Effects on Cellular Growth.” J. Biomed. Mater. Res., 39 630–636 (1998)
Subramani, S, Lee, JM, Cheong, IW, Kim, JH, “Synthesis and Characterization of Water-Borne Crosslinked Silylated Polyurethane Dispersions.” J. Appl. Polym. Sci., 98 620–631 (2005)
Melchiors, M, Blum, H, Noble, KL, “Method of Producing Oxidative Drying Urethane-Modified Polyester Dispersions and Their Use.” US Patent 6,620,893 B1, 2003
Wicks, DA, Wicks, ZW, “Autoxidizable Urethane Resins.” Prog. Org. Coat., 54 145–149 (2005)
Joshi, RG, Provder, T, Ziemer, P, Mao, WJ, Shen, WD, Jones, FN, “Investigation of the Effect of Precoalescence or Postcoalescence Crosslinking on Film Formation, Properties, and Latex Morphology.” J. Coat. Technol. Res., 6 47–65 (2009)
Zhang, XY, Liu, YH, Huang, H, Li, YJ, Chen, HQ, “The Diacetone Acrylamide Crosslinking Reaction and Its Control of Core-Shell Polyacrylate Latices at Ambient Temperature.” J. Appl. Polym. Sci., 123 1822–1832 (2012)
Okamoto, Y, Hasegawa, Y, Yoshino, F, “Urethane/Acrylic Composite Polymer Emulsions.” Prog. Org. Coat., 29 175–182 (1996)
Hori, M, Nishida, R, Takaya, Y, Nakayama, Y, Sugishima, M, “Resinous Compositions for a Water Paint.” US Patent 5,614,582, 1997
Nakayama, Y, “Curing of Paint Films with Film-Penetrative Crosslinker at Ambient Temperature.” Prog. Org. Coat., 31 105–112 (1997)
Nakayama, Y, “Development of Novel Aqueous Coatings Which Meet the Requirements of Ecology-Conscious Society: Novel Cross-Linking System Based on Carbonyl-Hydrazide Reaction and Its Applications.” Prog. Org. Coat., 51 280–299 (2004)
Li, XR, Wang, XR, Shen, YD, Lai, XJ, Wang, R, Lv, HY, Fan, HB, “Synthesis and Characterization of Self-Crosslinked Polyurethane/Polyacrylate Composite Emulsion Based on Carbonyl-Hydrazide Reaction.” J. Polym. Res., 20 270 (2013)
Pajerski, Anthony, D, Heights, B, “Aqueous Dispersions of Polyurethane Compositions with Ketone-Hydrazide.” EP Patent 2,210,908 A1, 2007
Zhu, XL, Zhang, QS, Liu, LL, Kong, XZ, Feng, SY, “Synthesis and Characterization of a New Compound Bearing Ketone and Hydroxyl groups for Preparation of Ambient Temperature Self-Crosslinking Waterborne Polyurethanes.” Prog. Org. Coat., 59 324–330 (2007)
Zhao, J, Shen, YD, Lai, XJ, “Film-Forming Mechanism and Properties of Ketone Hydrazine Crosslinked and Silane Coupled Waterborne Polyurethane.” Acta. Polym. Sin., 9 1122–1128 (2010)
Zhang, M, Wu, YJ, Wu, HY, Zhang, QS, “Study on Reactive Polydimethylsiloxane-Modified Waterborne Polyurethanes.” J. Polym. Res., 19 9807 (2012)
Chen, DH, Sun, DC, “Synthesis and Application of EDA-Di(Diacetone Propionamido) in Room Temperature Self-Crosslinking.” CIESC J., 64 1112 (2013)
He, LN, Sun, DC, “Synthesis of High-Solid Content Sulfonate-Type Polyurethane Dispersion by Pellet Process.” J. Appl. Polym. Sci., 127 2823–2831 (2013)
Sun, DC, Dong, DQ, “High Solid Content Polyurethane Dispersions with Bimodal Particle Size Distribution.” J. Chem. Eng. Chin. Univ., 25 248–253 (2011)
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We gratefully acknowledge the financial support of Guangdong Province Scientific and Technological Foundation (Grant No. 2012A080105011).
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Liao, M., Sun, D. Synthesis and characterization of ambient-temperature self-crosslinked waterborne polyurethanes with a novel diol chain extender bearing two ketone groups. J Coat Technol Res 13, 667–676 (2016). https://doi.org/10.1007/s11998-015-9773-1
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DOI: https://doi.org/10.1007/s11998-015-9773-1