Synthesis, characterization, and micellization of pH-responsive poly(4-vinylpyridine)-block-poly(methacrylic acid) four-armed star-shaped block copolymers

Feng Xu; Shu-Zhen Zheng; Yan-Ling Luo; Ting-Ting Chen

Macromolecular Research, Vol.21, No.9, 977-986, September, 2013

DOI10.1007/s13233-013-1112-8 Export Citation

Synthesis, characterization, and micellization of pH-responsive poly(4-vinylpyridine)-block-poly(methacrylic acid) four-armed star-shaped block copolymers

Feng Xu^†, Shu-Zhen Zheng, Yan-Ling Luo^†, and Ting-Ting Chen

Key Laboratory of Macromolecular Science of Shaanxi Province, School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi’an, 710062, P. R. China

E-mail:,

pH-sensitive poly(4-vinylpyridine)-block-poly(methacrylic acid) (P4VP-b-PMAA) four-armed star-shaped block copolymers were synthesized by two-step atom transfer radical polymerization (ATRP), followed by hydrolysis of P4VP-b-poly(tert-butyl methacrylate) (P4VP-b-PtBMA). The chemical structure and molecular weight of the as-synthesized block copolymers were characterized by Fourier transform infrared spectrometry (FTIR), nuclear magnetic resonance (1H and 13C NMR), and gel permeation chromatography (GPC) determinations. The solution behavior was investigated by surface tension technique, ultraviolet visible (UV-vis) transmittance, transmission electron microscopy (TEM), dynamic light scattering (DLS), and zeta potentials measurements. The experimental results indicated that the copolymers can spontaneously assemble into spherical-shaped core-shell micelle aggregates, with a critical micelle concentration (CMC) about 200 mg L?1, hydrodynamic diameters from 90 to 210 nm, depending on the environmental pH values and compositional ratios. The transmittance measurements revealed that the block copolymers produce evident phase transition in aqueous solution at pH from 6.5 to 7.0. Zeta potential data revealed high micelle stability. The as-synthesized block copolymers are anticipated to find their applications in the realms of specific drug release, metal loading and heterogeneous catalysis.

Keywords:star-shaped copolymers;atom transfer radical polymerization (ATRP);self-assembly;pH-sensitivity;micellization

[References]

Zhang SF, Hu N, Ni ZB, Yang JZ, Chen MQ, Petrochem. Technol., 37, 350 (2008)
Jiao Z, Wang X, Chen ZM, Polym. Bull., 17, 78 (2010)
Zheng PW, Jiang XW, Zhang X, Zhang WQ, Shi LQ, Langmuir, 22(22), 9393 (2006)
Zhang WQ, Shi LQ, Ma RJ, An YL, Xu YL, Wu K, Macromolecules, 38(21), 8850 (2005)
Chen MQ, Zhang M, Zhang K, Liu XY, Yang C, Acta Polym. Sin., 5, 673 (2004)
Ueda J, Kamigaito M, Sawamoto M, Macromolecules, 31(20), 6762 (1998)
Angot S, Murthy KS, Taton D, Gnanou Y, Macromolecules, 31(21), 7218 (1998)
Zhang X, Xia JH, Matyjaszewski K, Macromolecules, 33(7), 2340 (2000)
Xia JH, Zhang X, Matyjaszewski K, Macromolecules, 32(13), 4482 (1999)
Baek KY, Kamigaito M, Sawamoto M, Macromolecules, 34(2), 215 (2001)
Bosman AW, Heumann A, Klaerner G, Benoit D, Frechet JMJ, Hawker CJ, J. Am. Chem. Soc., 123(26), 6461 (2001)
Bosman AW, Vestberg R, Heumann A, Frechet JMJ, Hawker CJ, J. Am. Chem. Soc., 125(3), 715 (2003)
Pispas S, Poulos Y, Hadjichristidis N, Macromolecules, 31(13), 4177 (1998)
Kanaoka S, Nakata S, Yamaoka H, Macromolecules, 35(12), 4564 (2002)
Tsitsilianis C, Graff S, Remp P, Eur. Polym. J., 27, 243 (1991)
Fazeli N, Taromi FA, J. Polym. Sci. A: Polym. Chem., 41(1), 135 (2003)
Tsitsilianis C, Papanagopoulos D, Lutz P, Polymer, 19, 3745 (1995)
Beyer FL, Gido SP, Poulos Y, Avgeropoulos A, Hadjichristidis N, Macromolecules, 30(8), 2373 (1997)
Kanaoka S, Omura T, Sawamoto M, Higashimura T, Macromolecules, 25, 6407 (1992)
Percec V, Barboiu B, Macromolecules, 28(23), 7970 (1995)
Matyjaszewski K, Xia JH, Chem. Rev., 101(9), 2921 (2001)
Angot S, Murthy KS, Taton D, Gnanou Y, Macromolecules, 33(20), 7261 (2000)
Wu XF, Fraser CL, Macromolecules, 33(11), 4053 (2000)
Valenti TW, Cherry DS, Currie RJ, Neves RJ, Jones JW, Mair R, Kane CM, Environ. Toxicol. Chem., 25, 2512 (2006)
Arico F, Vavasori A, Liu Z, Jiang T, Pure Appl. Chem., 84, 411 (2012)
Li JB, Ren J, Cao Y, Yuan WZ, React. Funct. Polym., 69(12), 870 (2009)
Astafieva I, Khougaz K, Eisenberg A, Macromolecules, 28(21), 7127 (1995)
Gohy JF, Varshney SK, Jerome R, Macromolecules, 34(10), 3361 (2001)
Arimura H, Ohya Y, Ouchi T, Biomacromolecules, 6(2), 720 (2005)
Sommer C, in Structure and Dynamics of Charged Worm-Like Micelles, Swiss Federal Institute of Technology Zurich (Dissertation), Swiss, 2001, p 34.
Yang YQ, Zheng LS, Guo XD, Qian Y, Zhang LJ, Biomacromolecules, 12(1), 116 (2011)
Liu FT, Eisenberg A, J. Am. Chem. Soc., 125(49), 15059 (2003)
Luo SZ, Liu SY, Xu J, Liu H, Zhu ZY, Jiang M, Wu C, Macromolecules, 39(13), 4517 (2006)
Topouza D, Orfanou K, Pispas S, J. Polym. Sci. A: Polym. Chem., 42(24), 6230 (2004)

[Referenced By]

[1] Zhang SF, Hu N, Ni ZB, Yang JZ, Chen MQ, Petrochem. Technol., 37, 350 (2008)

[2] Jiao Z, Wang X, Chen ZM, Polym. Bull., 17, 78 (2010)

[3] Zheng PW, Jiang XW, Zhang X, Zhang WQ, Shi LQ, Langmuir, 22(22), 9393 (2006)

[4] Zhang WQ, Shi LQ, Ma RJ, An YL, Xu YL, Wu K, Macromolecules, 38(21), 8850 (2005)

[5] Chen MQ, Zhang M, Zhang K, Liu XY, Yang C, Acta Polym. Sin., 5, 673 (2004)

[6] Ueda J, Kamigaito M, Sawamoto M, Macromolecules, 31(20), 6762 (1998)

[7] Angot S, Murthy KS, Taton D, Gnanou Y, Macromolecules, 31(21), 7218 (1998)

[8] Zhang X, Xia JH, Matyjaszewski K, Macromolecules, 33(7), 2340 (2000)

[9] Xia JH, Zhang X, Matyjaszewski K, Macromolecules, 32(13), 4482 (1999)

[10] Baek KY, Kamigaito M, Sawamoto M, Macromolecules, 34(2), 215 (2001)

[11] Bosman AW, Heumann A, Klaerner G, Benoit D, Frechet JMJ, Hawker CJ, J. Am. Chem. Soc., 123(26), 6461 (2001)

[12] Bosman AW, Vestberg R, Heumann A, Frechet JMJ, Hawker CJ, J. Am. Chem. Soc., 125(3), 715 (2003)

[13] Pispas S, Poulos Y, Hadjichristidis N, Macromolecules, 31(13), 4177 (1998)

[14] Kanaoka S, Nakata S, Yamaoka H, Macromolecules, 35(12), 4564 (2002)

[15] Tsitsilianis C, Graff S, Remp P, Eur. Polym. J., 27, 243 (1991)

[16] Fazeli N, Taromi FA, J. Polym. Sci. A: Polym. Chem., 41(1), 135 (2003)

[17] Tsitsilianis C, Papanagopoulos D, Lutz P, Polymer, 19, 3745 (1995)

[18] Beyer FL, Gido SP, Poulos Y, Avgeropoulos A, Hadjichristidis N, Macromolecules, 30(8), 2373 (1997)

[19] Kanaoka S, Omura T, Sawamoto M, Higashimura T, Macromolecules, 25, 6407 (1992)

[20] Percec V, Barboiu B, Macromolecules, 28(23), 7970 (1995)

[21] Matyjaszewski K, Xia JH, Chem. Rev., 101(9), 2921 (2001)

[22] Angot S, Murthy KS, Taton D, Gnanou Y, Macromolecules, 33(20), 7261 (2000)

[23] Wu XF, Fraser CL, Macromolecules, 33(11), 4053 (2000)

[24] Valenti TW, Cherry DS, Currie RJ, Neves RJ, Jones JW, Mair R, Kane CM, Environ. Toxicol. Chem., 25, 2512 (2006)

[25] Arico F, Vavasori A, Liu Z, Jiang T, Pure Appl. Chem., 84, 411 (2012)

[26] Li JB, Ren J, Cao Y, Yuan WZ, React. Funct. Polym., 69(12), 870 (2009)

[27] Astafieva I, Khougaz K, Eisenberg A, Macromolecules, 28(21), 7127 (1995)

[28] Gohy JF, Varshney SK, Jerome R, Macromolecules, 34(10), 3361 (2001)

[29] Arimura H, Ohya Y, Ouchi T, Biomacromolecules, 6(2), 720 (2005)

[30] Sommer C, in Structure and Dynamics of Charged Worm-Like Micelles, Swiss Federal Institute of Technology Zurich (Dissertation), Swiss, 2001, p 34.

[31] Yang YQ, Zheng LS, Guo XD, Qian Y, Zhang LJ, Biomacromolecules, 12(1), 116 (2011)

[32] Liu FT, Eisenberg A, J. Am. Chem. Soc., 125(49), 15059 (2003)

[33] Luo SZ, Liu SY, Xu J, Liu H, Zhu ZY, Jiang M, Wu C, Macromolecules, 39(13), 4517 (2006)

[34] Topouza D, Orfanou K, Pispas S, J. Polym. Sci. A: Polym. Chem., 42(24), 6230 (2004)