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

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Abstract

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.

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References

  • Bae, S.E., J.S. Son, K. Park, and D.K. Han, 2009, Fabrication of covered porous PLGA microspheres using hydrogen peroxide for controlled drug delivery and regenerative medicine, J. Control. Release 133, 37–43.

    Article  Google Scholar 

  • Chung, H.J., H.K. Kim, J.J. Yoon, and T.G. Park, 2006, Heparin immobilized porous PLGA microspheres for angiogenic growth factor delivery, Pharm. Res. 23, 1835–1841.

    Article  Google Scholar 

  • Deng, R.H., S.Q. Liu, J.Y. Li, Y.G. Liao, J. Tao, and J.T. Zhu, 2012, Mesoporous block copolymer nanoparticles with tailored structures by hydrogen-bonding-assisted self-assembly, Adv. Mater. 24, 1889–1893.

    Article  Google Scholar 

  • Ding, S.Y., J. Gao, Q. Wang, Y. Zhang, W.G. Song, C.Y. Su, and W. Wang, 2011, Construction of covalent organic framework for catalysis: Pd/COF-LZU1 in Suzuki-Miyaura coupling reaction, J. Am. Chem. Soc. 133, 19816–19822.

    Article  Google Scholar 

  • Durie, S., K. Jerabek, C. Mason, and D.C. Sherrington, 2002, One-pot synthesis of branched poly (styrene divinylbenzene) suspension polymerized resins, Macromolecules 35, 9665–9672.

    Article  Google Scholar 

  • Gokmen, M.T. and F.E. Du Prez, 2012, Porous polymer particles-A comprehensive guide to synthesis, characterization, functionalization and applications, Prog. Polym. Sci. 37, 365–405.

    Article  Google Scholar 

  • Gokmen, M.T., W. Van Camp, P.J. Colver, S. Bon, and F.E. Du Prez, 2009, Fabrication of porous “clickable” polymer beads and rods through generation of high internal phase emulsion (HIPE) droplets in a simple microfluidic device, Macromolecules 42, 9289–9294.

    Article  Google Scholar 

  • Gong, X., W. Wen, and P. Sheng, 2009, Microfluidic fabrication of porous polymer microspheres: dual reactions in single droplets, Langmuir 25, 7072–7077.

    Article  Google Scholar 

  • Hudson, D., 1999, Matrix assisted synthetic transformations: A mosaic of diverse contributions. I. The pattern emerges, J. Comb. Chem. 1, 333–360.

    Article  Google Scholar 

  • Jang, T.S., E.J. Lee, H.E. Kim, and Y.H. Koh, 2012, Hollow porous poly(epsilon-caprolactone) microspheres by emulsion solvent extraction, Mater. Lett. 72, 157–159.

    Article  Google Scholar 

  • Jose, A.J., S. Ogawa, and M. Bradley, 2005, Tuning the pore size and surface area of monodisperse Poly (Methyl Acrylate) beads via parallel seeded polymerization, Polymer 46, 2880–2888.

    Article  Google Scholar 

  • Kim, M.R., S. Lee, J.K. Park, and K.Y. Cho, 2010, Golf ballshaped PLGA microparticles with internal pores fabricated by simple O/W emulsion, Chem. Commun. 46, 7433–7435.

    Article  Google Scholar 

  • Klose, D., F. Siepmann, K. Elkharraz, S. Krenzlin, and J. Siepmann, 2006, How porosity and size affect the drug release mechanisms from PLGA-based microparticles, Int. J. Pharm. 314, 198–206.

    Article  Google Scholar 

  • Kong, S.F., X.F. Wen, P.H. Pi, J. Cheng, and Z.R. Yang, 2008, Preparation and characterization of magnetic porous γ-Fe2O3/P(St-DVD-MAA) polymer microspheres, Acta. Polym. Sin. 2, 168–173.

    Article  Google Scholar 

  • Li, B.Y., X. Huang, L.Y. Liang, and B.E. Tan, 2010, Synthesis of uniform microporous polymer nanoparticles and their applications for hydrogen storage, J. Mater. Chem. 20, 7444–7450.

    Article  Google Scholar 

  • Liu, S.Q., R.H. Deng, W.K. Li, and J.T. Zhu, 2012, Polymer microparticles with controllable surface textures generated through interfacial instabilities of emulsion droplets, Adv. Funct. Mater. 22, 1692–1697.

    Article  Google Scholar 

  • Loxley, A. and B. Vincent, 1998, Preparation of poly (methylmethacrylate) microcapsules with liquid cores, J. Colloid Interf. Sci. 208, 49–62.

    Article  Google Scholar 

  • Okubo, M., T. Fujibayashi, and A. Terada, 2005, Synthesis of micron-sized, monodisperse polymer particles of disc-like and polyhedral shapes by seeded dispersion polymerization, Colloid Polym. Sci. 283, 793–798.

    Article  Google Scholar 

  • Rao, T.P., R.S. Praveen, and S. Daniel, 2004, Styrene-divinyl benzene copolymers: synthesis, characterization, and their role in inorganic trace analysis, Crit. Rev. Anal. Chem. 34, 177–193.

    Article  Google Scholar 

  • Shi, X.D., L. Sun, and Z.H. Gan, 2011, Formation mechanism of solvent-induced porous PLA microspheres, Acta. Polym. Sin. 8, 866–873.

    Article  Google Scholar 

  • Sing, K.S.W., D.H. Everett, R.A.W. Haul, L. Moscou, R.A. Pierotti, J. Rouquerol, and T. Siemieniewska, 1985, Reporting physisorption data for gas/solid systems with special reference to the determination of surface area and porosity, Pure Appl. Chem. 57, 603–619.

    Article  Google Scholar 

  • Slater, M., M. Snauko, F. Svec, and J.M. Fréchet, 2006, “Click chemistry” in the preparation of porous polymer-based particulate stationary phases for μ-HPLC separation of peptides and proteins, Anal. Chem. 78, 4969–4975.

    Article  Google Scholar 

  • Svec, F. and J.M. Fréchet, 1996, New designs of macroporous polymers and supports: from separation to biocatalysis, Science 273, 205–211.

    Article  Google Scholar 

  • Tanaka, T., Y. Komatsu, T. Fujibayashi, H. Minami, and M. Okubo, 2010, A novel approach for preparation of micrometersized, monodisperse dimple and hemispherical polystyrene particles, Langmuir 26, 3848–3853.

    Article  Google Scholar 

  • Wang, N.X., Y.G. Liao, R.H. Deng, S.Q. Liu, N. Cao, B.E. Tan, J.T. Zhu, and X.L. Xie, 2012, Polymer-inorganic hybrid microparticles with hierarchical structures formed by interfacial instabilities of emulsion droplets, Soft Matter 8, 2697–2704.

    Article  Google Scholar 

  • Watanabe, T., T. Ono, and Y. Kimura, 2011, Continuous fabrication of monodisperse polylactide microspheres by droplet-to-particle technology using microfluidic emulsification and emulsion-solvent diffusion, Soft Matter 7, 9894–9897.

    Article  Google Scholar 

  • Wood, C.D., B.E. Tan, A. Trewin, F. Su, M.J. Rosseinsky, D. Bradshaw, Y. Sun, L. Zhou, and A.I. Cooper, 2008, Microporous organic polymers for methane storage, Adv. Mater. 20, 1916–1921.

    Article  Google Scholar 

  • Wu, D.C., F. Xu, B. Sun, R.W. Fu, H.K. He, and K. Matyjaszewski, 2012, Design and preparation of porous polymers, Chem. Rev. 112, 3959–4015.

    Article  Google Scholar 

  • Yabu, H., T. Higuchi, K. Ijiro, and M. Shimomura, 2005, Spontaneous formation of polymer nanoparticles by goodsolvent evaporation as a nonequilibrium process, Chaos 15, 047505.

    Article  Google Scholar 

  • Yow, H.N., and A.F. Routh, 2008, Colloidal buckets formed via internal phase separation, Soft Matter 4, 2080–2085.

    Article  Google Scholar 

  • Zou, S.W., H. Liu, Y. Yang, Z.J. Wei, and C.Y. Wang, 2013, Multihollow nanocomposite microspheres with tunable pore structures by templating Pickering double emulsions, React. Funct. Polym. 73, 1231–1241.

    Article  Google Scholar 

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Correspondence to Jintao Zhu.

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Liu, S., Cai, M., Deng, R. et al. Fabrication of porous polymer microparticles with tunable pore size and density through the combination of phase separation and emulsion-solvent evaporation approach. Korea-Aust. Rheol. J. 26, 63–71 (2014). https://doi.org/10.1007/s13367-014-0007-3

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