Fabrication of porous polymer microparticles with tunable pore size and density through the combination of phase separation and emulsion-solvent evaporation approach

Shanqin Liu; Mingle Cai; Renhua Deng; Jianying Wang; Ruijing Liang; Jintao Zhu

Korea-Australia Rheology Journal, Vol.26, No.1, 63-71, February, 2014

Shanqin Liu¹, Mingle Cai¹, Renhua Deng¹, Jianying Wang¹, Ruijing Liang¹, and Jintao Zhu^{1, 2, †}

¹Key Laboratory for Large-Format Battery Materials and System of Ministry of Education, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology (HUST), Wuhan, 430074, P. R. China
²National Engineering Center for Nanomedicine, HUST, Wuhan, 430074, P. R. China

E-mail:

A facile and versatile route to prepare porous polymer microparticles with tunable pore size and density through the combination of phase separation and emulsion-solvent evaporation method is demonstrated. When volatile organic solvent (e.g., chloroform) diffuses through the aqueous phase containing poly(vinyl alcohol) (PVA) and evaporates, n-hexadecane (HD) and polystyrene (PS) in oil-in-water emulsion droplets occur to phase separate due to the incompatibility between PS and HD, ultimately yielding microparticles with porous structures. Interestingly, density of the pores (pore number) on the shell of microparticles can be tailored from one to hundreds by simply varying the HD concentration and/or the rate of solvent evaporation. Moreover, this versatile approach for preparing porous microparticles with tunable pore size and density can be applied to other types of hydrophobic polymers, organic solvents, and alkanes, which will find potential applications in the fields of pharmaceutical, catalyst carrier, separation, and diagnostics.

Keywords:porous microparticles;emulsion droplets;solvent evaporation;phase separation;pore size

[References]

Bae SE, Son JS, Park K, Han DK, J.Control. Release., 133, 37 (2009)
Chung HJ, Kim HK, Yoon JJ, Park TG, Pharm. Res., 23, 1835 (2006)
Deng RH, Liu SQ, Li JY, Liao YG, Tao J, Zhu JT, Adv. Mater., 24(14), 1889 (2012)
Ding SY, Gao J, Wang Q, Zhang Y, Song WG, Su CY, Wang W, J. Am. Chem. Soc., 133(49), 19816 (2011)
Durie S, Jerabek K, Mason C, Sherrington DC, Macromolecules, 35(26), 9665 (2002)
Gokmen MT, Du Prez FE, Prog. Polym. Sci., 37, 365 (2012)
Gokmen MT, Van Camp W, Colver PJ, Bon SAF, Du Prez FE, Macromolecules, 42(23), 9289 (2009)
Gong XQ, Wen WJ, Sheng P, Langmuir, 25(12), 7072 (2009)
Hudson D, J.Comb. Chem., 1, 333 (1999)
Jang TS, Lee EJ, Kim HE, Koh YH, Mater. Lett., 72, 157 (2012)
Jose AJ, Ogawa S, Bradley M, Polymer, 46(9), 2880 (2005)
Kim MR, Lee S, Park JK, Cho KY, Chem. Commun., 46, 7433 (2010)
Klose D, Siepmann F, Elkharraz K, Krenzlin S, Siepmann J, Int. J. Pharm., 314, 198 (2006)
Kong SF, Wen XF, Pi PH, Cheng J, Yang ZR, Acta. Polym. Sin., 2, 168 (2008)
Li BY, Huang X, Liang LY, Tan BE, J. Mater. Chem., 20, 7444 (2010)
Liu SQ, Deng RH, Li WK, Zhu JT, Adv. Funct. Mater., 22(8), 1692 (2012)
Loxley A, Vincent B, J. Colloid Interface Sci., 208(1), 49 (1998)
Okubo M, Fujibayashi T, Terada A, Colloid Polym. Sci., 283, 793 (2005)
Rao TP, Praveen RS, Daniel S, Crit. Rev. Anal. Chem., 34, 177 (2004)
Shi XD, Sun L, Gan ZH, Acta. Polym. Sin., 8, 866 (2011)
Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T, Pure Appl.Chem., 57, 603 (1985)
Slater M, Snauko M, Svec F, Frechet JM, Anal. Chem., 78, 4969 (2006)
Svec F, Frechet JM, Science, 273(5272), 205 (1996)
Tanaka T, Komatsu Y, Fujibayashi T, Minami H, Okubo M, Langmuir, 26(6), 3848 (2010)
Wang NX, Liao YG, Deng RH, Liu SO, Cao N, Tan BE, Zhu JT, Xie XL, Soft Matter., 8, 2697 (2012)
Watanabe T, Ono T, Kimura Y, Soft Matter., 7, 9894 (2011)
Wood CD, Tan B, Trewin A, Su F, Rosseinsky MJ, Bradshaw D, Sun Y, Zhou L, Cooper AI, Adv. Mater., 20(10), 1916 (2008)
Wu DC, Xu F, Sun B, Fu RW, He HK, Matyjaszewski K, Chem. Rev., 112(7), 3959 (2012)
Yabu H, Higuchi T, Ijiro K, Shimomura M, Chaos., 15, 047505 (2005)
Yow HN, Routh AF, Soft Matter., 4, 2080 (2008)
Zou SW, Liu H, Yang Y, Wei ZJ, Wang CY, React.Funct. Polym., 73, 1231 (2013)

[1] Bae SE, Son JS, Park K, Han DK, J.Control. Release., 133, 37 (2009)

[2] Chung HJ, Kim HK, Yoon JJ, Park TG, Pharm. Res., 23, 1835 (2006)

[3] Deng RH, Liu SQ, Li JY, Liao YG, Tao J, Zhu JT, Adv. Mater., 24(14), 1889 (2012)

[4] Ding SY, Gao J, Wang Q, Zhang Y, Song WG, Su CY, Wang W, J. Am. Chem. Soc., 133(49), 19816 (2011)

[5] Durie S, Jerabek K, Mason C, Sherrington DC, Macromolecules, 35(26), 9665 (2002)

[6] Gokmen MT, Du Prez FE, Prog. Polym. Sci., 37, 365 (2012)

[7] Gokmen MT, Van Camp W, Colver PJ, Bon SAF, Du Prez FE, Macromolecules, 42(23), 9289 (2009)

[8] Gong XQ, Wen WJ, Sheng P, Langmuir, 25(12), 7072 (2009)

[9] Hudson D, J.Comb. Chem., 1, 333 (1999)

[10] Jang TS, Lee EJ, Kim HE, Koh YH, Mater. Lett., 72, 157 (2012)

[11] Jose AJ, Ogawa S, Bradley M, Polymer, 46(9), 2880 (2005)

[12] Kim MR, Lee S, Park JK, Cho KY, Chem. Commun., 46, 7433 (2010)

[13] Klose D, Siepmann F, Elkharraz K, Krenzlin S, Siepmann J, Int. J. Pharm., 314, 198 (2006)

[14] Kong SF, Wen XF, Pi PH, Cheng J, Yang ZR, Acta. Polym. Sin., 2, 168 (2008)

[15] Li BY, Huang X, Liang LY, Tan BE, J. Mater. Chem., 20, 7444 (2010)

[16] Liu SQ, Deng RH, Li WK, Zhu JT, Adv. Funct. Mater., 22(8), 1692 (2012)

[17] Loxley A, Vincent B, J. Colloid Interface Sci., 208(1), 49 (1998)

[18] Okubo M, Fujibayashi T, Terada A, Colloid Polym. Sci., 283, 793 (2005)

[19] Rao TP, Praveen RS, Daniel S, Crit. Rev. Anal. Chem., 34, 177 (2004)

[20] Shi XD, Sun L, Gan ZH, Acta. Polym. Sin., 8, 866 (2011)

[21] Sing KSW, Everett DH, Haul RAW, Moscou L, Pierotti RA, Rouquerol J, Siemieniewska T, Pure Appl.Chem., 57, 603 (1985)

[22] Slater M, Snauko M, Svec F, Frechet JM, Anal. Chem., 78, 4969 (2006)

[23] Svec F, Frechet JM, Science, 273(5272), 205 (1996)

[24] Tanaka T, Komatsu Y, Fujibayashi T, Minami H, Okubo M, Langmuir, 26(6), 3848 (2010)

[25] Wang NX, Liao YG, Deng RH, Liu SO, Cao N, Tan BE, Zhu JT, Xie XL, Soft Matter., 8, 2697 (2012)

[26] Watanabe T, Ono T, Kimura Y, Soft Matter., 7, 9894 (2011)

[27] Wood CD, Tan B, Trewin A, Su F, Rosseinsky MJ, Bradshaw D, Sun Y, Zhou L, Cooper AI, Adv. Mater., 20(10), 1916 (2008)

[28] Wu DC, Xu F, Sun B, Fu RW, He HK, Matyjaszewski K, Chem. Rev., 112(7), 3959 (2012)

[29] Yabu H, Higuchi T, Ijiro K, Shimomura M, Chaos., 15, 047505 (2005)

[30] Yow HN, Routh AF, Soft Matter., 4, 2080 (2008)

[31] Zou SW, Liu H, Yang Y, Wei ZJ, Wang CY, React.Funct. Polym., 73, 1231 (2013)