Colloidal Behavior of Polystyrene-Based Copolymer Microgels Composed of a Hydrophilic Hydrogel Layer

Kong Soo Kim; Brian Vincent; Terence Cosgrove

Journal of Industrial and Engineering Chemistry, Vol.12, No.1, 91-97, January, 2006

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Colloidal Behavior of Polystyrene-Based Copolymer Microgels Composed of a Hydrophilic Hydrogel Layer

Kong Soo Kim^†, Brian Vincent¹, and Terence Cosgrove¹

Department of Chemical Engineering, Chung-buk University, Cheong Ju, Chung buk 361-763, Korea
¹School of Chemistry University of Bristol Cantock's Close Bristol BS8 ITS, UK

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Polystyrene (PSt)-based copolymer colloidal microgels consisting of a hydrophilic hydrogel layer, such as poly(methacrylic acid) (PMAA) or poly(N-isopropyl acrylamide) (PNIPAM), were synthesized through emulsifier-free polymerization. The morphology and particle size of the microgel particles were characterized using a combination of TEM and photon correlation spectroscopy (PCS). The microgel particles consisted of a hydrophobic PSt-core and a hydrophilic PMAA and PNIPAM shell. When the microgels were characterized for their pH- and temperature-responsive behaviors by PCS, the hydrodynamic diameter of the microgel particles composed of St/MAA/NIPAM gradually increased below pH 4.5 and above pH 7. LCSTs of PNIPAM in the microgels were barely affected by different molar ratios of St/MAA/NIPAM; in addition, the shrinking transition of the microgels, which were composed of St/MAA/NIPAM, shifted to higher region than did the LCST of PNIPAM. The electrophoretic mobility and zeta potential for the microgel particles were found to be negative, and a marked maximum negative value occurred at around pH 5. The colloidal stability of the microgel particles was very sensitive to the concentration of the KCl solution and to the temperature.

Keywords:emulsifier-free polymerization;copolymer microgels;pH/temperature-sensitive microgels;core-shell polymerparticles;colloidal stability

[References]

Snowden MJ, Chowdhry BZ, Vincent B, Morris GE, J. Chem. Soc.-Faraday Trans., 92, 5013 (1996)
Saunders BR, Crowther HM, Vincent B, Macromolecules, 30(3), 482 (1997)
Makino K, Agata H, Ohshima H, J. Colloid Interface Sci., 230(1), 128 (2000)
Kratz K, Hellewg T, Eimer W, Colloids Surf. A: Physicochem. Eng. Asp., 170, 137 (2000)
Chun HJ, Lee SB, Nam SY, Ryu SH, Jung SY, Shin SH, Cheong SI, Rhim JW, J. Ind. Eng. Chem., 11(4), 556 (2005)
Eeckman F, Mos AJ, Amighi K, Int. J. Pharm., 241, 113 (2002)
Zhang XZ, Zhuo RX, Cui JZ, Zhang JT, Int. J. Pharm., 235, 43 (2002)
Chung JE, Yakoyama M, Yamato M, Aoyagi Y, Sakurai Y, Okang T, J. Control. Release, 62, 115 (1999)
Dilgimen AS, Mustafaeva Z, Demchenko M, Kaneko T, Osada Y, Mustafaeva M, Biomaterials, 22, 2383 (2001)
Kondo A, Higashitani, J. Colloid Interface Sci., 150, 345 (1991)
Revilla J, Elaissari A, Carriere P, Pichot C, J. Colloid Interface Sci., 180(2), 405 (1996)
Duracher D, Elaissari A, Mallet F, Pichot C, Langmuir, 16(23), 9002 (2000)
Yasui M, Shiroya T, Fujimoto K, Kawaguchi H, Colloids Surf. B: Biointerfaces, 8, 311 (1997)
Daubresse C, Grandfils C, Jrome R, Ph T, Colloid Polym. Sci., 274, 482 (1996)
Kim JH, Ballauff M, Colloid Polym. Sci., 277, 1210 (1999)
Kuboto K, Fujishige S, Ando I, J. Phys. Chem., 94, 5154 (1990)
Pelton RH, Chibante P, Colloids Surf. A: Physicochem. Eng. Asp., 20, 247 (1986)
Pelton RH, Pelton HM, Morphesis A, Rowell RL, Langmuir, 5, 816 (1989)
Makino K, Yamamoto S, Fujimoto K, Kawaguchi H, Ohshima H, J. Colloid Interface Sci., 166(1), 251 (1994)
Hoshino F, Fujimoto T, Kawaguchi H, Ohtsuka Y, Polym. J., 19, 241 (1987)
Wang YM, Feng LX, Pan CY, J. Appl. Polym. Sci., 74(6), 1502 (1999)
Loxley A, Vincent B, Colloid Polym. Sci., 275, 1108 (1997)
Duracher D, Sauzedde F, Elaissari A, Perrin A, Pichot C, Colloid Polym. Sci., 276, 219 (1998)
Kim KS, Vincent B, Polym. J., 37, 1 (2005)
Kim KS, Kim MH, Cho SH, J. Ind. Eng. Chem., 11, 763 (2005)
Nabzar L, Duracher D, Elaissari A, Chauveteau G, Pichot C, Langmuir, 14(18), 5062 (1998)
Bastos D, Nieves de las FJ, Colloid Polym. Sci., 272, 592 (1994)
Jayasuriya RM, El-Aasser MS, Vanderhoff JW, J. Polym Sci. Polym. Chem., 23, 2819 (1985)
Reerink H, Overbeek JTG, Discuss. Faraday Soc., 18, 74 (1950)
Verweg EJW, Overbeek JTG, Theory of the Stability of Lyophobic Colloids, Elsevier; Amsterdam (1948)
Rubio-Hermandez FJ, J. Non-Equilib. Thermodyn., 2, 153 (1996)
Sung JH, Cho MS, Choi HJ, Jhon MS, J. Ind. Eng. Chem., 10(7), 1217 (2004)

[Referenced By]

[1] Snowden MJ, Chowdhry BZ, Vincent B, Morris GE, J. Chem. Soc.-Faraday Trans., 92, 5013 (1996)

[2] Saunders BR, Crowther HM, Vincent B, Macromolecules, 30(3), 482 (1997)

[3] Makino K, Agata H, Ohshima H, J. Colloid Interface Sci., 230(1), 128 (2000)

[4] Kratz K, Hellewg T, Eimer W, Colloids Surf. A: Physicochem. Eng. Asp., 170, 137 (2000)

[5] Chun HJ, Lee SB, Nam SY, Ryu SH, Jung SY, Shin SH, Cheong SI, Rhim JW, J. Ind. Eng. Chem., 11(4), 556 (2005)

[6] Eeckman F, Mos AJ, Amighi K, Int. J. Pharm., 241, 113 (2002)

[7] Zhang XZ, Zhuo RX, Cui JZ, Zhang JT, Int. J. Pharm., 235, 43 (2002)

[8] Chung JE, Yakoyama M, Yamato M, Aoyagi Y, Sakurai Y, Okang T, J. Control. Release, 62, 115 (1999)

[9] Dilgimen AS, Mustafaeva Z, Demchenko M, Kaneko T, Osada Y, Mustafaeva M, Biomaterials, 22, 2383 (2001)

[10] Kondo A, Higashitani, J. Colloid Interface Sci., 150, 345 (1991)

[11] Revilla J, Elaissari A, Carriere P, Pichot C, J. Colloid Interface Sci., 180(2), 405 (1996)

[12] Duracher D, Elaissari A, Mallet F, Pichot C, Langmuir, 16(23), 9002 (2000)

[13] Yasui M, Shiroya T, Fujimoto K, Kawaguchi H, Colloids Surf. B: Biointerfaces, 8, 311 (1997)

[14] Daubresse C, Grandfils C, Jrome R, Ph T, Colloid Polym. Sci., 274, 482 (1996)

[15] Kim JH, Ballauff M, Colloid Polym. Sci., 277, 1210 (1999)

[16] Kuboto K, Fujishige S, Ando I, J. Phys. Chem., 94, 5154 (1990)

[17] Pelton RH, Chibante P, Colloids Surf. A: Physicochem. Eng. Asp., 20, 247 (1986)

[18] Pelton RH, Pelton HM, Morphesis A, Rowell RL, Langmuir, 5, 816 (1989)

[19] Makino K, Yamamoto S, Fujimoto K, Kawaguchi H, Ohshima H, J. Colloid Interface Sci., 166(1), 251 (1994)

[20] Hoshino F, Fujimoto T, Kawaguchi H, Ohtsuka Y, Polym. J., 19, 241 (1987)

[21] Wang YM, Feng LX, Pan CY, J. Appl. Polym. Sci., 74(6), 1502 (1999)

[22] Loxley A, Vincent B, Colloid Polym. Sci., 275, 1108 (1997)

[23] Duracher D, Sauzedde F, Elaissari A, Perrin A, Pichot C, Colloid Polym. Sci., 276, 219 (1998)

[24] Kim KS, Vincent B, Polym. J., 37, 1 (2005)

[25] Kim KS, Kim MH, Cho SH, J. Ind. Eng. Chem., 11, 763 (2005)

[26] Nabzar L, Duracher D, Elaissari A, Chauveteau G, Pichot C, Langmuir, 14(18), 5062 (1998)

[27] Bastos D, Nieves de las FJ, Colloid Polym. Sci., 272, 592 (1994)

[28] Jayasuriya RM, El-Aasser MS, Vanderhoff JW, J. Polym Sci. Polym. Chem., 23, 2819 (1985)

[29] Reerink H, Overbeek JTG, Discuss. Faraday Soc., 18, 74 (1950)

[30] Verweg EJW, Overbeek JTG, Theory of the Stability of Lyophobic Colloids, Elsevier; Amsterdam (1948)

[31] Rubio-Hermandez FJ, J. Non-Equilib. Thermodyn., 2, 153 (1996)

[32] Sung JH, Cho MS, Choi HJ, Jhon MS, J. Ind. Eng. Chem., 10(7), 1217 (2004)