Abstract
In this study, gradient acrylate latex particles were synthesized by gradient copolymerization. n-Butyl acrylate (BA) and methyl methacrylate (MMA) were used as co-monomers, dodecyl diphenyl ether sodium disulfonate as the emulsifier, and potassium persulfate as the initiator. The technique involved the continuous addition of one monomer mixture into a stirred tank containing another monomer mixture. Their microstructure and properties were analyzed by nuclear magnetic resonance (NMR), gel permeation chromatography (GPC), differential scanning calorimetry (DSC), atomic force microscopy (AFM), transmission electron microscopy (TEM), and particle size analysis. 1H-NMR spectra show a gradual change in the chemical composition with the growth of molecular chains. The gradient polymer latexes, the instantaneous copolymer composition of which varies as the polymerization proceeds, are obtained. GPC analyses show that the aggregated molecular chain in the BA-centered latex particle experiences a process from dominant BA to MMA with changes in the monomer's feed composition during the polymerization. Particle size and TEM analyses show that the increasing latex size agrees well with the gradient growth pattern. DSC analyses show that the gradient latex particles exhibit only one broadened and ambiguous glass transition region. AFM analyses indicate no obvious microphase segregation occurs in the gradient latex particles, further verifying that the gradient microstructure is obtained.
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Geoffrey, H, Ralph, M, Block Polymers of Monovinyl Aromatic Hydro-Carbons and Conjugated Dienes. USP: 3265765, 1966-08-09
Pakula, T, Matyjaszewski, K, “Copolymers with Controlled Distribution of Comonomers Along the Chain, 1. Structure, Thermodynamics and Dynamic Properties of Gradient Copolymers, Computer Simulation.” Macromol. Theory Simul., 5 (5) 987–1006 (1996)
Qin, S, Saget, J, Pyun, J, Jia, S, Kowalewaski, T, Matyjaszewski, K, “Regioregular Head-to-Tail Poly(4-alkylquinoline)s: Synthesis, Characterization, Self-Organization, Photophysics, and Electroluminescence of New n-Type Conjugated Polymers.” Macromolecules, 36 (24) 8969–8977 (2003)
Gray, MK, Zhou, H, Nguyen, ST, Torkelson, JM, “Synthesis and Glass Transition Behavior of High Molecular Weight Styrene/4-Acetoxystyene and Styrene/4-Hydroxystyrene Gradient Copolymers Made via Nitroxide-Mediated Controlled Radical Polymerization.” Macromolecules, 37 (15) 5586–5591 (2004)
Okabe, S, Seno, K, Kanaoka, S, “Micellization Study on Block and Gradient Copolymer Aqueous Solutions by DLS and SANS.” Macromolecules, 39 (4) 1592–1597 (2006)
Christopher, LH, Wong, JK, Torkelson, JM, “Comparison of Critical Micelle Concentrations of Gradient Copolymer and Block Copolymer in Homopolymer: Novel Characterization by Intrinsic Fluorescence.” Macromolecules, 40 (16) 5631–5633 (2007)
Kim, J, Mok, MM, Sandoval, RW, Woo, DJ, Torkelson, JM, “Uniquely Broad Glass Transition Temperatures of Gradient Copolymers Relative to Random and Block Copolymers Containing Repulsive Comonomers.” Macromolecules, 39 (18) 6152–6160 (2006)
Jiang, R, Jin, Q, Li, B, Ding, D, Wickham, RA, Shi, AC, “Phase Behavior of Gradient Copolymers.” Macromolecules, 41 (14) 5457–5465 (2008)
Lefebvre, MD, De La Cruz, MO, Shull, KR, “Phase Segregation in Gradient Copolymer Melts.” Macromolecules, 37 (3) 1118–1123 (2004)
Michelle, MM, Pujari, S, Torkelson, JM, “Microphase Separation and Shear Alignment of Gradient Copolymers: Melt Rheology and Small-Angle X-Ray Scattering Analysis.” Macromolecules, 41 (16) 5818–5829 (2008)
Michelle, MM, Kim, J, Torkelson, JM, “Gradient Copolymers with Broad Glass Transition Temperature Regions: Design of Purely Interphase Compositions for Damping Applications.” J. Polym. Sci. B Polym. Phys., 46 (1) 48–58 (2008)
Matyjaszewski, K, Michael, JZ, Arehart, SV, Greszta, D, Pakula, T, “Gradient Copolymers by Atom Transfer Radical Copolymerization.” J. Phys. Org. Chem., 13 (12) 775–786 (2000)
Arzamendi, G, Asua, JM, “Monomer Addition Policies for Copolymer Composition Control in Semicontinuous Emulsion Copolymerization.” J. Appl. Polym. Sci., 38 (11) 2019–2036 (1989)
Vicente, M, Leiza, JR, Asua, JM, “Control of Microstructural Properties in Emulsion Polymerization Systems.” Macromol. Symp., 182 (1) 291–303 (2002)
Bassett, DR, Hoy, KL, Emulsion Polymers and Emulsion Polymerization. ACS Symposium Series. American Chemical Society, Washington, DC, 1981
Ziegler, MJ, Matyjaszewski, K, “Atom Transfer Radical Copolymerization of Methyl Methacrylate and n-Butyl Acrylate.” Macromolecules, 34 (3) 415–424 (2001)
Arehart, SV, Matyjaszewski, K, “Atom Transfer Radical Copolymerization of Styrene and n-Butyl Acrylate.” Macromolecules, 32 (7) 2221–2231 (1999)
Dettmer, CM, Gray, MK, Torkelson, JM, Nguyen, ST, “Synthesis and Functionalization of ROMP-Based Gradient Copolymers of 5-Substituted Norbornenes.” Macromolecules, 37 (15) 5504–5512 (2004)
Gray, MK, Zhou, H, Nguyen, ST, Torkelson, JM, “Differences in Enthalpy Recovery of Gradient and Random Copolymers of Similar Overall Composition: Styrene/4-Methylstyrene Copolymers Made by Nitroxide-Mediated Controlled Radical Polymerization.” Polymer, 45 (14) 4777–4786 (2004)
Boerner, HG, Duran, D, Matyjaszewski, K, da Silva, M, Sheiko, SS, “Synthesis of Molecular Brushes with Gradient in Grafting Density by Atom Transfer Polymerization.” Macromolecules, 35 (9) 3387–3394 (2002)
Gray, MK, Nguyen, ST, Zhou, H, Torkelson, JM, “Gradient Copolymers Produced via Nitroxide-Mediated Controlled Radical Polymerization.” Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.), 43 (2) 112–113 (2002)
Tonelli, AE, NMR Spectroscopy and Polymer Microstructure the Conformational Connection. VCH, New York, 1989
Brar, AS, Kaur, J, “2D NMR Studies of Acrylonitrile-Methyl Acrylate Copolymers.” Eur. Polym. J., 41 (10) 2278–2289 (2005)
Kotani, Y, Kamigaito, M, Sawamoto, M, “Living Random Copolymerization of Styrene and Methyl Methacrylate with a Ru(II) Complex and Synthesis of ABC-Type “Block-Random” Copolymers.” Macromolecules, 31 (17) 5582–5587 (1998)
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The authors gratefully acknowledge the financial support from the National Natural Science Foundation of China (No. 50803017).
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Zhang, X., Wei, X., Yang, W. et al. Characterization and properties of gradient polyacrylate latex particles by gradient emulsion polymerization. J Coat Technol Res 9, 765–774 (2012). https://doi.org/10.1007/s11998-012-9422-x
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DOI: https://doi.org/10.1007/s11998-012-9422-x