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The reinforcing effect of crosslinkable waterborne polyurethane/polysiloxane composite emulsion by aqueous sol–gel method

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Abstract

A highly branched polysiloxane (S2) was prepared by an aqueous sol–gel process and used as an underlying crosslinker to modify silanized waterborne polyurethane (WPUS), and a novel crosslinked waterborne polyurethane (WPU)/polysiloxane composite with low VOC features was obtained. The good dispersibility of polysiloxane (S2) was proved by both TEM and DLS analyses, implying that the polysiloxane had an excellent intermiscibility with the WPU. The larger silsesquioxane network in the composite was proved by XPS, which was generated from the condensation of the Si–OH groups of polysiloxane and WPUS. On the basis of tensile results, the content of polysiloxane had a significant impact on the mechanical properties. The reinforcing and toughening synergy effect was found in the composite with a low concentration of S2. According to micrographs of the fracture surface, the dominating toughening mechanism was dependent on microcracks, while the high concentration of polysiloxane turned into silica particles in the WPU matrix, resulting in force concentration and degradation of the mechanical properties. However, the Young’s modulus increased with the increasing content of S2. Additionally, the incorporation of the crosslinked silsesquioxane structure also improved the hydrophobic properties and thermal stability of the composite.

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References

  1. Chen, CJ, Tseng, IH, Tsai, MH, Hsu, AW, Liu, TC, Huang, SL, “Composition, Thermal and Tensile Properties of Polyurethane-urea-silica Hybrids.” RSC Adv., 3 (25) 9729–9738 (2013)

    Article  CAS  Google Scholar 

  2. Kim, BK, Seo, JW, Jeong, HM, “Morphology and Properties of Waterborne Polyurethane/clay Nanocomposites.” Eur. Polym. J., 39 (1) 85–91 (2003)

    Article  CAS  Google Scholar 

  3. Chung, YC, Kang, KS, Chun, BC, “Lateral Sol-gel Cross-linking of Polyurethane Using the a Grafted Triethoxysilyl Group.” J. Sol-Gel Sci. Technol., 72 (3) 543–552 (2014)

    Article  CAS  Google Scholar 

  4. Chung, YC, Park, HS, Choi, JW, Chun, BC, “Characterization and Low Temperature Test of the Flexibly Crosslinked Polyurethane Copolymer by Poly(dimethylsiloxane).” High Perform. Polym., 24 (3) 200–209 (2012)

    Article  CAS  Google Scholar 

  5. Rahman, MM, Hasneen, A, Kim, HD, Lee, WK, “Preparation and Properties of Polydimethylsiloxane (PDMS)/polytetramethyleneadipate Glycol (PTAd)-based Waterborne Polyurethane Adhesives: Effect of PDMS Molecular Weight and Content.” J. Appl. Polym. Sci., 125 (1) 88–96 (2012)

    Article  CAS  Google Scholar 

  6. Hwang, HD, Kim, HJ, “Enhanced Thermal and Surface Properties of Waterborne UV-curable Polycarbonate-based Polyurethane (Meth)acrylate Dispersion by Incorporation of Polydimethylsiloxane.” React. Funct. Polym., 71 (6) 655–665 (2011)

    Article  CAS  Google Scholar 

  7. Sardon, H, Irusta, L, Santamaría, P, Fernándze-Berridi, MJ, “Thermal and Mechanical Behavior of Self-curable Waterborne Hybrid Polyurethanes Functionalized with (3-Aminopropyl)triethoxysilane (APTES).” J. Polym. Res., 19 (9) 9956 (2012)

    Article  Google Scholar 

  8. Sardon, H, Irusta, L, Fernándze-Berridi, MJ, Lansalot, M, Bourgeat-Lami, E, “Synthesis of Room Temperature Self-Curable Waterborne Hybrid Polyurethane Functionalized with (3-Aminopropyl)triethoxysilane (APTES).” Polymer, 51 (22) 5051–5057 (2010)

    Article  CAS  Google Scholar 

  9. Zhang, S, Chen, Z, Guo, M, Bai, H, Liu, X, “Synthesis and Characterization of Waterborne UV-curable Polyurethane Modified with Side-chain Triethoxysilane and Colloidal Silica.” Colloid Surf. A, 468 1–9 (2015)

    Article  CAS  Google Scholar 

  10. Sardon, H, Irusta, L, González, A, Fernándze-Berridi, MJ, “Waterborne Hybrid Polyurethane Coatings Functionalized with (3-Aminopropyl)triethoxylsilane: Adhesion Properties.” Prog. Org. Coat., 76 (9) 1230–1235 (2013)

    Article  CAS  Google Scholar 

  11. Nanda, AK, Wicks, DA, Madbouly, SA, Otaigbe, JU, “Nanostructured Polyurethane/pOSS Hybrid Aqueous Dispersions Prepared by Homogeneous Solution Polymerization.” Macromolecules, 39 (20) 7037–7043 (2006)

    Article  CAS  Google Scholar 

  12. Wu, Y, Du, Z, Wang, H, Cheng, X, “Synthesis of Aqueous Highly Branched Silica Sol as Underlying Crosslinker for Corrosion Protection.” Prog. Org. Coat., 111 381–388 (2017)

    Article  CAS  Google Scholar 

  13. Brinker, CJ, Scherer, GW, Sol-gel Science: The Physics and Chemistry of Sol-gel Processing. Academic, London (1990)

    Google Scholar 

  14. Bertoluzza, A, Fagnano, C, Antonietta Morelli, M, Gottardi, V, Guglielmi, M, “Raman and Infrared Spectra on Silica Gel Evolving Toward Glass.” J. Non-Cryst Solids, 48 (1) 117–128 (1982)

    Article  CAS  Google Scholar 

  15. Depla, A, Lesthaeghe, D, van Erp, TS, Aerts, A, Houthoofd, K, Fan, F, Li, C, Speybroeck, VV, Waroquier, M, Kirschhock, CEA, Martens, JA, “29Si NMR and UV-Raman Investigation of Initial Oligomerization Reaction Pathways in Acid-Catalyzed Silica Sol-Gel Chemistry.” J. Phys. Chem., 115 (9) 3562–3571 (2011)

    CAS  Google Scholar 

  16. Zerda, TW, Artaki, I, Jonas, J, “Study of Polymerization Processes in Acid and Base Catalyzed Silica Sol-gels.” J. Non-Cryst. Solids, 81 (3) 365–379 (1986)

    Article  CAS  Google Scholar 

  17. Gottardi, V, Guglielmi, M, Bertoluzza, A, Fagnano, C, Morelli, MA, “Further Investigation on Raman Spectra of Silica Gel Evolving Toward Glass.” J. Non-Cryst. Solids, 63 (1–2) 71–80 (1984)

    Article  CAS  Google Scholar 

  18. Li, Q, Guo, L, Qiu, T, Xiao, W, Du, D, Li, X, “Synthesis of Waterborne Polyurethane Containing Alkoxysilane Side Groups and the Properties of the Hybrid Coating Films.” Appl. Surf. Sci., 377 66–74 (2016)

    Article  CAS  Google Scholar 

  19. Yu, K, Wang, M, Qian, K, Lu, X, Sun, J, “The Synergy Effect of Graphene/SiO2 Hybrid Materials on Reinforcing and Toughening Epoxy Resin.” Fiber Polym., 17 (3) 453–459 (2016)

    Article  CAS  Google Scholar 

  20. Hourston, DJ, Lane, S, Zhang, HX, “Toughened Thermoplastics: 2. Impact Properties and Fracture Mechanisms of Rubber Modified Poly(butylene terephthalates).” Polymer, 32 (12) 2215–2220 (1991)

    Article  CAS  Google Scholar 

  21. Chen, JH, Rong, MZ, Ruan, WH, Zhang, MQ, “Interfacial Enhancement of Nano-SiO2/Polypropylene Composites.” Compos. Sci. Technol., 69 (2) 252–259 (2009)

    Article  CAS  Google Scholar 

  22. Agag, T, Koga, T, Takeichi, T, “Studies on Thermal and Mechanical Properties of Polyimide-clay Nanocomposites.” Polymer, 42 (8) 3399–3408 (2001)

    Article  CAS  Google Scholar 

  23. Wetzel, B, Rosso, P, Haupert, F, Friedrich, K, “Epoxy Nanocomposites–Fracture and Toughening Mechanisms.” Eng. Fract. Mech., 73 (16) 2375–2398 (2006)

    Article  Google Scholar 

  24. Li, C, Wu, J, Zhao, J, Zhao, D, Fan, Q, “Effect of Inorganic Phase on Polymeric Relaxation Dynamics in PMMA/Silica Hybrids Studied by Dielectric Analysis.” Eur. Polym. J., 40 (8) 1807–1814 (2004)

    Article  CAS  Google Scholar 

  25. Seo, JW, Kim, BK, “Preparations and Properties of Waterborne Polyurethane/nanosilica Composites.” Polym. Bull., 54 (1–2) 123–128 (2005)

    Article  CAS  Google Scholar 

  26. Subramani, S, Lee, JM, Cheong, IW, Kim, JH, “Synthesis and Characterization of Water-borne Crosslinked Silylated Polyurethane Dispersions.” J. Appl. Polym Sci., 98 (2) 620–631 (2005)

    Article  CAS  Google Scholar 

  27. Jena, KK, Sahoo, S, Narayan, R, Aminabhavi, TM, Raju, K, “Novel Hyperbranched Waterborne Polyurethane-urea/silica Hybrid Coatings and Their Characterizations.” Polym. Int., 60 (10) 1504–1513 (2011)

    Article  CAS  Google Scholar 

  28. Wang, G, Ma, G, Hou, C, Guan, T, Ling, L, Wang, B, “Preparation and Properties of Waterborne Polyurethane/nanosilica Composites: A Diol as Extender with Triethoxysilane Group.” J. Appl. Polym. Sci., 131 (15) 338–347 (2014)

    Google Scholar 

Download references

Acknowledgment

This study was supported by plan of Science and Technology Department of Chongqing Province, China (No. cstc2018jcyjA2568).

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Correspondence to Yan Wu.

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Wu, Y., Wu, J. & Feng, Y. The reinforcing effect of crosslinkable waterborne polyurethane/polysiloxane composite emulsion by aqueous sol–gel method. J Coat Technol Res 17, 243–253 (2020). https://doi.org/10.1007/s11998-019-00264-9

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