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Synthesis of (Sty-co-BA-AA) latexes including ZnO and TiO2 nanoparticle by miniemulsion polymerization

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Abstract

Herein, it is reported that synthesis of poly(styrene-co-butyl acrylate) latexes containing ZnO and TiO2 nanoparticles was carried out using miniemulsion polymerization. The synthesized latexes and films cast from them were characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), scanning electron microscopy energy dispersive X-ray (SEM-EDAX), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Stress–strain and DMA analysis was performed for the mechanical analysis of the films prepared from latexes. The particle sizes of the latexes were about 60 nm for pure latex and latex only containing ZnO and TiO2, while the particle size for latex containing nanoparticle mixture was measured as 120 nm. XRD, SEM-EDAX, and TEM analysis results showed that the nanoparticles were well dispersed in latex. When the mechanical analysis results were compared, latex films including 2% ZnO nanoparticles were found to be stronger. DMA analysis showed that the glass transition temperature (Tg) values of the polymers were between 0 and 10°C and the nanoparticles were not effective in changing the Tg values. Latex films were exposed to 254 nm UV light to determine their yellowing. According to the colorimetric measurement, ZnO nanoparticle-embedded films were found to be more resistant to yellowing.

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References

  1. Erbil, Y, Vinyl Acetate Emulsion Polymerization and Copolymerization with Acrylic Monomers. CRC Press, Boca Raton (2000)

    Book  Google Scholar 

  2. Lovell, PA, El-Aasser, MS, Emulsion Polymerization and Emulsion Polymers. Wiley, Hoboken (1997)

    Google Scholar 

  3. Dieter. U, Takamura, K, Polymer Dispersions and Their Industrial Applications. Wiley VCH Verlag GmbH & Co, KGaA (2002)

    Google Scholar 

  4. Man, YK, Mu, LY, Wang, Y, Lin, SH, Rempel, GL, Pan, QM, “Synthesis and Characterization of Rutile Titanium Dioxide/Polyacrylate Nanocomposites for Applications in Ultraviolet Light-Shielding Materials.” Polym. Comp., 36 (1) 8–16 (2015)

    Article  CAS  Google Scholar 

  5. Aquirre, M, Paulis, M Leiza, JR,  "Waterborne Acrylic/CeO2 Nanocomposites for UV Blocking Clear Coats," In: Khan, S, Akhtor, K (Eds) Cerium Oxide—Applications and Attributes, Intechopen (2018)

  6. Tang, EJ, Liu, H, Sun, LM, Zheng, EL, Cheng, GX, “Fabrication of Zinc Oxide/poly(styrene) Grafted Nanocomposite Latex and its Dispersion.” Europ. Polym. J., 43 (10) 4210–4218 (2007)

    Article  CAS  Google Scholar 

  7. Hu, J, Chen, M, Wu, LM, “Organic-inorganic Nanocomposites Synthesized via Miniemulsion Polymerization.” Polym. Chem., 2 (4) 760–772 (2011)

    Article  CAS  Google Scholar 

  8. Hu, J, Zhou, Y, “The Properties of Nano(ZnO-CeO2)@polysiloxane Core–shell Microspheres and Their Application for Fabricating Optical Diffusers.” Appl. Surf. Sci., 365 166–170 (2016)

    Article  CAS  Google Scholar 

  9. Chimenti, S, Vega, JM, Aguirre, M, García-Lecina, E, Díez, JA, Grande, H-J, Paulis, M, Leiza, JR, “Effective Incorporation of ZnO Nanoparticles by Miniemulsion Polymerization in Waterborne Binders for Steel Corrosion Protection.” J. Coat. Technol. Res., 14 (4) 829–839 (2017)

    Article  CAS  Google Scholar 

  10. Delibas, A, Yildiz, U, Tauer, K, “Composite Latex Production with High Solid Content.” J. Appl. Polym. Sci., 136 18 (2019)

    Article  CAS  Google Scholar 

  11. Tang, EJ, Dong, SY, “Preparation of Styrene Polymer/ZnO Nanocomposite Latex via Miniemulsion Polymerization and its Antibacterial Property.” Colloid Polym. Sci., 287 (9) 1025–1032 (2009)

    Article  CAS  Google Scholar 

  12. Diaconu, G, Paulis, M, Leiza, JR, “High Solids Content Waterborne Acrylic/Montmorillonite Nanocomposites by Miniemulsion Polymerization.” Macromol. React. Eng., 2 (1) 80–89 (2008)

    Article  CAS  Google Scholar 

  13. Zengeni, E, Hartmann, PC, Pasch, H, “Highly Filled Polystyrene/Laponite Hybrid Nanoparticles Prepared Using the Ad-Miniemulsion Polymerisation Technique.” Macromol. Chem. Phys., 214 (1) 62–75 (2013)

    Article  CAS  Google Scholar 

  14. Bonnefond, A, Paulis, M, Bon, SAF, Leiza, JR, “Surfactant-free Miniemulsion Polymerization of n-BA/S Stabilized by NaMMT: Films with Improved Water Resistance.” Langmuir, 29 (7) 2397–2405 (2013)

    Article  CAS  Google Scholar 

  15. Herrera, NN, Letoffe, JM, Putaux, JL, David, L, Bourgeat-Lami, E, “Aqueous Dispersions of Silane-functionalized Laponite Clay Platelets. A First Step toward the Elaboration of Water-based Polymer/Clay Nanocomposites.” Langmuir, 20 (5) 1564–1571 (2004)

    Article  CAS  Google Scholar 

  16. Kang, BA, Schrade, A, Xu, Y, Chan, YT, Ziener, U, “Synthesis and Characterization of Dually Labeled Pickering-type Stabilized Polymer Nanoparticles in a Downscaled Miniemulsion System.” Langmuir, 28 (25) 9347–9354 (2012)

    Article  CAS  Google Scholar 

  17. Yılmaz, O, Cheaburu, CN, Gülümser, G, Vasile, C, “On the Stability and Properties of the Polyacrylate/Na-MMT Nanocomposite Obtained by Seeded Emulsion Polymerization.” Europ. Polym. J., 48 (10) 1683–1695 (2012)

    Google Scholar 

  18. Ruggerone, R, Plummer, CJG, Herrera, NN, Bourgeat-Lami, E, Månson, J-AE, “Highly Filled Polystyrene–laponite Nanocomposites Prepared by Emulsion Polymerization.” Europ. Polym. J., 45 (3) 621–629 (2009)

    Article  CAS  Google Scholar 

  19. Plummer, CJG, Ruggerone, R, Bourgeat-Lami, E, Manson, JAE, “Small Strain Mechanical Properties of Latex-based Acrylic Nanocomposite Films.” Polym., 52 (9) 2009–2015 (2011)

    Article  CAS  Google Scholar 

  20. Diaconu, G, Micusik, M, Bonnefond, A, Paulis, M, Leiza, JR, “Macroinitiator and Macromonomer Modified Montmorillonite for the Synthesis of Acrylic/MMT Nanocomposite Latexes.” Macromol., 42 (9) 3316–3325 (2009)

    Article  CAS  Google Scholar 

  21. Sheibat-Othman, N, Cenacchi-Pereira, AM, Dos Santos, AM, Bourgeat-Lami, E, “A Kinetic Investigation of Surfactant-free Emulsion polymerization of Styrene Using Laponite Clay Platelets as Stabilizers.” J. Polym. Sci. Part A-Polym. Chem., 49 (22) 4771–4784 (2011)

    Article  CAS  Google Scholar 

  22. Christopher, G, Anbu Kulandainathan, M, Harichandran, G, “Highly Dispersive Waterborne Polyurethane/ZnO Nanocomposites for Corrosion Protection.” J. Coat. Technol. Res., 12 (4) 657–667 (2015)

    Article  CAS  Google Scholar 

  23. Gu, X, Chen, G, Zhao, M, Watson, SS, Nguyen, T, Chin, JW, Martin, JW, “Critical Role of Particle/Polymer Interface in Photostability of Nano-filled Polymeric Coatings.” J. Coat. Technol. Res., 9 (3) 251–267 (2012)

    Article  CAS  Google Scholar 

  24. Danková, M, Kalendová, A, Machotová, J, “Waterborne Coatings based on Acrylic Latex Containing Nanostructured ZnO as an Active Additive.” J. Coat. Technol. Res., 17 (2) 517–529 (2020)

    Article  CAS  Google Scholar 

  25. Chou, IC, Lee, CF, Chiu, WY, “Preparation of Novel Suspensions of ZnO/Living Block Copolymer Latex Nanoparticles via Pickering Emulsion Polymerization and Their Long Term Stability.” J. Polym. Sci. Part A: Polym. Chem., 49 (16) 3524–3535 (2011)

    Article  CAS  Google Scholar 

  26. Erdem, B, Sudol, ED, Dimonie, VL, El-Aasser, MS, “Encapsulation of Inorganic Particles via Miniemulsion polymerization. I. Dispersion of Titanium Dioxide Particles in Organic Media Using OLOA 370 as Stabilizer.” J. Polym. Sci. Part A: Polym. Chem., 38 (24) 4419–4430 (2000)

    Article  CAS  Google Scholar 

  27. Erdem, B, Sudol, ED, Dimonie, VL, El-Aasser, MS, “Encapsulation of Inorganic Particles via Miniemulsion Polymerization. II. Preparation and Characterization of Styrene Miniemulsion Doplets Containing TiO2 Particles.” J. Polym. Sci. Part A: Polym. Chem., 38 (24) 4431–4440 (2000)

    Article  CAS  Google Scholar 

  28. Zhang, M, Gao, G, Li, C-Q, Liu, F-Q, “Titania-Coated Polystyrene Hybrid Microballs Prepared with Miniemulsion Polymerization.” Langmuir, 20 (4) 1420–1424 (2004)

    Article  CAS  Google Scholar 

  29. Wu, YF, Zhang, Y, Xu, JX, Chen, M, Wu, LM, “One-Step Preparation of PS/TiO2 Nanocomposite Particles via Miniemulsion Polymerization.” J. Colloid Interf. Sci., 343 (1) 18–24 (2010)

    Article  CAS  Google Scholar 

  30. Gonzalez, E, Bonnefond, A, Barrado, M, Barrasa, AMC, Asua, JM, Leiza, JR, “Photoactive Self-cleaning Polymer Coatings by TiO2 Nanoparticle Pickering Miniemulsion Polymerization.” Chem. Eng. J., 281 209–217 (2015)

    Article  CAS  Google Scholar 

  31. Ma, Q, Izu, N, Masuda, Y, “Ceria Polymer Hybrid Nanoparticles and Assembled Films for Coating Applications.” ACS Appl. Nano Mater., 1 (5) 2112–2119 (2018)

    Article  CAS  Google Scholar 

  32. İncel, A, Güner, T, Parlak, O, Demir, MM, “Null Extinction of Ceria@Silica Hybrid Particles: Transparent Polystyrene Composites.” ACS Appl. Mater. Interfaces, 7 (49) 27539–27546 (2015)

    Article  CAS  Google Scholar 

  33. Aguirre, M, Paulis, M, Leiza, JR, “Particle Nucleation and Growth in Seeded Semibatch Miniemulsion Polymerization of Hybrid CeO2/Acrylic Latexes.” Polym., 55 (3) 752–761 (2014)

    Article  CAS  Google Scholar 

  34. Zgheib, N, Putaux, J-L, Thill, A, D’Agosto, F, Lansalot, M, Bourgeat-Lami, E, “Stabilization of Miniemulsion Droplets by Cerium Oxide Nanoparticles: a Step Toward the Elaboration of Armored Composite Latexes.” Langmuir, 28 (14) 6163–6174 (2012)

    Article  CAS  Google Scholar 

  35. Garnier, J, Warnant, J, Lacroix-Desmazes, P, Dufils, P-E, Vinas, J, van Herk, A, “Sulfonated Macro-RAFT Agents for the Surfactant-free Synthesis of Cerium Oxide-based Hybrid Latexes.” J. Colloid Interf. Sci., 407 273–281 (2013)

    Article  CAS  Google Scholar 

  36. Bonnefond, A, Ibarra, M, Gonzalez, E, Barrado, M, Chuvilin, A, Maria Asua, J, Ramon Leiza, J, “Photocatalytic and Magnetic Titanium Dioxide/Polystyrene/Magnetite Composite Hybrid Polymer Particles.” J. Polym. Sci. Part A: Polym. Chem., 54 (20) 3350–3356 (2016)

    Article  CAS  Google Scholar 

  37. Mori, Y, Kawaguchi, H, “Impact of Initiators in Preparing Magnetic Polymer Particles by Miniemulsion Polymerization.” Colloids Surf. B: Biointerfaces, 56 (1) 246–254 (2007)

    Article  CAS  Google Scholar 

  38. Staudt, T, Machado, TO, Vogel, N, Weiss, CK, Araujo, PHH, Sayer, C, Landfester, K, “Magnetic Polymer/Nickel Hybrid Nanoparticles via Miniemulsion Polymerization.” Macromol. Chem. Phys., 214 (19) 2213–2222 (2013)

    Article  CAS  Google Scholar 

  39. Kojima, Y, Usuki, A, Kawasumi, M, Okada, A, Fukushima, Y, Kurauchi, T, Kamigaito, O, “Mechanical Properties of Nylon 6-clay Hybrid.” J. Mater. Res., 8 (5) 1185–1189 (1993)

    Article  CAS  Google Scholar 

  40. Eren, M, Can, HK, “Preparation of Zinc Methacrylate-methylmethacrylate-butyl Acrylate Emulsions and Their Application in Exterior Paints.” Prog. Org. Coat., 135 424–437 (2019)

    Article  CAS  Google Scholar 

  41. Gholami, M, Shirzad-Siboni, M, Farzadkia, M, Yang, J-K, “Synthesis, Characterization, and Application of ZnO/TiO2 Nanocomposite for Photocatalysis of a Herbicide (Bentazon).” Desalin. Water Treat., 57 (29) 13632–13644 (2016)

    Article  CAS  Google Scholar 

  42. Aguirre, M, Barrado, M, Iturrondobeitia, M, Okariz, A, Guraya, T, Paulis, M, Leiza, JR, “Film Forming Hybrid Acrylic/ZnO Latexes with Excellent UV Absorption Capacity.” Chem. Eng. J., 270 300–308 (2015)

    Article  CAS  Google Scholar 

  43. Faucheu, J, Gauthier, C, Chazeau, L, Cavaille, JY, Mellon, V, Bourgeat-Lami, E, “Miniemulsion Polymerization for Synthesis of Structured Clay/Polymer Nanocomposites: Short Review and Recent Advances.” Polym., 51 (1) 6–17 (2010)

    Article  CAS  Google Scholar 

  44. Romo-Uribe, A, Arcos-Casarrubias, JA, Hernandez-Vargas, ML, Reyes-Mayer, A, Aguilar-Franco, M, Bagdhachi, J, “Acrylate Hybrid Nanocomposite Coatings Based on SiO2 Nanoparticles by In-situ Batch Emulsion Polymerization.” Prog. Org. Coat., 97 288–300 (2016)

    Article  CAS  Google Scholar 

  45. Youssef, A, El-Nagar, I, El-Torky, A and El-Hakim, AEFA, "Preparation and Characterization of PMMA Nanocomposites Based on ZnO-NPs for Antibacterial Packaging Applications." Proc. World Congress on New Technologies, (2019)

  46. Sonawane, SH, Teo, BM, Brotchie, A, Grieser, F, Ashokkumar, M, “Sonochemical Synthesis of ZnO Encapsulated Functional Nanolatex and Its Anticorrosive Performance.” Ind. & Eng. Chem. Res., 49 (5) 2200–2205 (2010)

    Article  CAS  Google Scholar 

  47. Lee, DI, “The Effects of Latex Coalescence and Interfacial Crosslinking on the Mechanical Properties of Latex Films.” Polym., 46 (4) 1287–1293 (2005)

    Article  CAS  Google Scholar 

  48. Pinprayoon, O, Saiani, A, Groves, R, Saunders, BR, “Particulate Ionomer Films Prepared from Dispersions of Crosslinked Polymer Colloids: a Structure–Property Study.” J. Colloid Interf. Sci., 336 (1) 73–81 (2009)

    Article  CAS  Google Scholar 

  49. Schellenberg, C, Tauer, K, Antonietti, M, “Film Formation of Polymeric Emulsions: Structure Set-up and the Pinhole Effect Characterized by Microscopic Techniques.” J. Dispersion Sci. Technol., 20 (1–2) 177–186 (1999)

    Article  CAS  Google Scholar 

  50. Samakande, A, Sanderson, RD, Hartmann, PC, “Encapsulated Clay Particles in Polystyrene by RAFT Mediated Miniemulsion Polymerization.” J. Polym. Sci. Part A: Polym. Chem., 46 (21) 7114–7126 (2008)

    Article  CAS  Google Scholar 

  51. Ruot, B, Plassais, A, Olive, F, Guillot, L, Bonafous, L, “TiO2-Containing Cement Pastes and Mortars: Measurements of the Photocatalytic Efficiency Using a Rhodamine B-based Colourimetric Test.” Solar Energy, 83 (10) 1794–1801 (2009)

    Article  CAS  Google Scholar 

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Acknowledgments

Thanks to Scientific Research Projects Unit of Yozgat Bozok University (Grant no. 6602c-FEF/16-12) for the financial support. Thanks to Dr. Ramazan Coşkun for his valuable comments.

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Correspondence to Ali Delibaş.

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Delibaş, A. Synthesis of (Sty-co-BA-AA) latexes including ZnO and TiO2 nanoparticle by miniemulsion polymerization. J Coat Technol Res 18, 717–727 (2021). https://doi.org/10.1007/s11998-020-00436-y

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