Coacervation Microencapsulation of CaCO₃ Particles with a Fluoropolymer by Pressure-induced Phase Separation of Supercritical Carbon Dioxide Solutions

Kenji Mishima, Haruo Yokota, Takafumi Kato, Tadashi Suetsugu, Xiuqin Wei, Keiichi Irie, Kenichi Mishima, Michihiro Fujiwara

Department of Chemical Engineering,Fukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka 814-0180, Japan.
Department of Chemical EngineeringFukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka 814-0180, Japan.
Department of Electronics Engineering and Computer Science, Fukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka 814-0180, Japan.
Department of Electronics Engineering and Computer ScienceFukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka 814-0180, Japan.
Department of Neuropharmacology, Fukuoka University, 8-19-1 Nanakuma Jonan-ku, Fukuoka 814-0180, Japan.

DOI: 10.4236/ampc.2012.24B047                

Abstract

 We report a method for the coacervation micro-encapsulation of several forms of CaCO₃ microparticles with the fluoropolymer poly(heptadecafluorodecyl acrylate) (poly (HDFDA)) by pressure-induced phase separation of a supercritical CO₂ solution.  A suspension of CaCO₃ in CO₂ and dissolved poly(HDFDA) were mixed in supercritical CO₂.  After the system pressure was slowly decreased to atmospheric pressure, the microcapsules were obtained.  Coacervation was achieved by the precipitation of poly(HDFDA) during the decrease in the pressure of CO₂; the solubility of poly(HDFDA) in CO₂ decreased with the pressure.  The structure and morphology of the microparticles were investigated by using a scanning electron microscope (SEM) and an electron probe microanalyzer (EPMA) equipped with a wavelength dispersive X-ray spectroscope (WDX).

Keywords

Component; Supercritical Carbon Dioxide; Microencapsulation; Coacervation; Fluoropolymer; Calcium Carbonate

Conflicts of Interest

The authors declare no conflicts of interest.

References

[1]	J. Jung and M. Perrut, “Particle design using supercritical fluids: Literature and patent survey,” The Journal of Supercritical Fluids, vol. 20, no. 3, pp.179-219, 2001. J. Clerk Maxwell, A Treatise on Electricity and Magnetism, 3rd ed., vol. 2. Oxford: Clarendon, 1892, pp.68–73.
[2]	S. D. Yeo and E. Kiran, “Formation of polymerparticles with supercriticalfluids: A review,” The Journal of Supercritical Fluids, vol. 34, no. 3, pp. 287-308, 2005.
[3]	E. Reverchon and R. Adami, “Nanomaterials and supercriticalfluids,” The Journal of Supercritical Fluids, vol. 37, no. 1, pp. 1-22, 2006.
[4]	J.W.Tom, P.G. Debenedetti, R. Jerome, “ Precipitation of Poly(L-lactic acid) and Composite Poly(L-lactic acid)-Pyrene Particles by Rapid Expansion of Supercritical Solutions.” J. Supercritical Fluids vol.7, 9,1994.
[5]	K. Mishima, K. Matsuyama, D. Tanabe, S. Yamauchi, T. J. Young, and K. P. Johnston, “Microencapsulation of proteins by rapid expansion of supercritical solution with a nonsolvent,” AIChE Journal, vol. 46, no. 4, pp. 857-865, 2000.
[6]	K. Mishima,”Biodegradable particle formation for drug and gene delivery using supercritical fluid and dense gas, “Advanced Drug Delivery Reviews, vol. 60, no. 3, pp. 411-432, 2008.
[7]	K. Matsuyama, K. Mishima, K. Hayashi, and H. Matsuyama, “Microencapsulation of TiO2 Nanoparticles with Polymer by Rapid Expansion of Supercritical Solution,” Journal of Nanoparticle Research, vol. 5, no. 1-2, pp. 87-95, 2003.
[8]	K. Matsuyama, K. Mishima, K. I. Hayashi, H. Ishikawa, H. Matsuyama, and T. Harada, “Formation of microcapsules of medicines by the rapid expansion of a supercritical solution with a nonsolvent,” Journal of Applied Polymer Science, vol. 89, no. 3, pp. 742-752, 2003.
[9]	K. Matsuyama and K. Mishima, “Coacervation microencapsulation of talc particles with a fluoropolymer by pressure-induced phase separation of supercritical carbon dioxide solutions,” Industrial and Engineering Chemistry Research, vol, 45, no. 18, pp. 6462-6168, 2006.
[10]	DeSimone, J. M.; Guan, Z.; Elsbernd, C. S. Synthesis of Fluoropolymers in Supercritical Carbon Dioxide. Science 257, 945-946,1992.
[11]	Chernyak, Y.; Henon, F.; Harris, R. B.; Gould, R. D.; Franklin, R. K.; Edwards, J. R.; DeSimone, J. M.; Carbonell, R. G. Formation of Perfluoropolyether Coatings by the Rapid Expansion of Supercritical Solutions (RESS) Process. Part 1: Experimental Results. Ind. Eng. Chem. Res. 2001, 40, 6118..
[12]	Blasig, A.; Shi, C. M.; Enick, R. M.; Thies, M. C. Effect of Concentration and Degree of Saturation on RESS of a CO2-soluble Fluoropolymer. Ind. Eng. Chem. Res. 2002, 41, 4976.
[13]	Mawson, S.; Johnston, K. P.; Combes, J. R.; DeSimone, J. M. Formation of Poly(1,1,2,2-tetrahydroperfluorodecyl acrylate) Submicron Fibers and Particles from Supercritical Carbon Dioxide Solutions. Macromolecules 1995, 28, 3182.
[14]	Luna-Barcenas, G.; Mawson, S.; Takishima, S.; DeSimone, J. M.; Sanchez, I. C.; Johnston, K. P. Phase Behavior of Poly(1,1-dihydroperfluorooctylacrylate) in Supercritical Carbon Dioxide. Fluid Phase Equilibria 1998, 146, 325.
[15]	Calvo, L.; Holmes, J. D.; Yates, M. Z.; Johnston, K. P. Steric Stabilization of Inorganic Suspensions in Carbon Dioxide. J. Supercritical Fluids 2000, 16, 247.
[16]	J. Lazko, Y. Popineau, J. Legrand, Soy Glycinin Microcapsules by Simple Coacervation Method. Colloids and Surfaces B: Biointerfaces 2004, 37, 1.