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
Erbil, Y, Vinyl Acetate Emulsion Polymerization and Copolymerization with Acrylic Monomers. CRC Press, Boca Raton (2000)
Lovell, PA, El-Aasser, MS, Emulsion Polymerization and Emulsion Polymers. Wiley, Hoboken (1997)
Dieter. U, Takamura, K, Polymer Dispersions and Their Industrial Applications. Wiley VCH Verlag GmbH & Co, KGaA (2002)
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)
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)
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)
Hu, J, Chen, M, Wu, LM, “Organic-inorganic Nanocomposites Synthesized via Miniemulsion Polymerization.” Polym. Chem., 2 (4) 760–772 (2011)
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)
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)
Delibas, A, Yildiz, U, Tauer, K, “Composite Latex Production with High Solid Content.” J. Appl. Polym. Sci., 136 18 (2019)
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)
Diaconu, G, Paulis, M, Leiza, JR, “High Solids Content Waterborne Acrylic/Montmorillonite Nanocomposites by Miniemulsion Polymerization.” Macromol. React. Eng., 2 (1) 80–89 (2008)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
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)
Mori, Y, Kawaguchi, H, “Impact of Initiators in Preparing Magnetic Polymer Particles by Miniemulsion Polymerization.” Colloids Surf. B: Biointerfaces, 56 (1) 246–254 (2007)
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)
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)
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)
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)
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)
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)
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)
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)
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)
Lee, DI, “The Effects of Latex Coalescence and Interfacial Crosslinking on the Mechanical Properties of Latex Films.” Polym., 46 (4) 1287–1293 (2005)
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)
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)
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)
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)
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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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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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DOI: https://doi.org/10.1007/s11998-020-00436-y