Preparation of high internal water-phase double emulsions stabilized by a single anionic surfactant for fabricating interconnecting porous polymer microspheres.

Herein we report a one-step method to prepare high internal water-phase double emulsions (W/O/W) via catastrophic phase inversion of water-in-oil high internal phase emulsions (W/O HIPEs) stabilized solely by 12-acryloxy-9-octadecenoic acid (AOA) through increasing the content of water phase. This is the first time for double emulsions to be stabilized solely by a single small molecular surfactant, which are usually costabilized by both hydrophilic and hydrophobic surfactants. After neutralized with ammonia, AOA is confirmed to be capable of stabilizing both W/O emulsions and O/W emulsions, which may account for its unique ability to stabilize double emulsions. The effects of different conditions (including changing the concentrations of AOA and salt (NaCl), pH value, the polarity of oils, the addition interval of water and stirring rate, etc.) on the formation and the stability of double emulsions as well as the inversion point have been investigated by using optical microscopy and conductivity monitoring. Finally, porous polymer microspheres with high interconnection (polyHIPE microspheres) were fabricated by γ-ray initiated polymerization of the as-prepared double emulsions composed of different monomers (styrene, or n-butyl acrylate, or methyl methacrylate), which have been confirmed by scanning electron microscopy. Our method is facile and effective for preparing high interconnecting porous polymer microspheres without tedious post-treatment of the products in common emulsion polymerization due to the use of polymerizable surfactant.

[1]  J. Cai,et al.  One-step formation of w/o/w multiple emulsions stabilized by single amphiphilic block copolymers. , 2012, Langmuir : the ACS journal of surfaces and colloids.

[2]  D. Burgess,et al.  Relationship between rheological properties and one-step W/O/W multiple emulsion formation. , 2010, Langmuir : the ACS journal of surfaces and colloids.

[3]  Filip Du Prez,et al.  Fabrication of porous "clickable" polymer beads and rods through generation of high internal phase emulsion (HIPE) droplets in a simple microfluidic device , 2009 .

[4]  D. Burgess,et al.  Influence of phase inversion on the formation and stability of one-step multiple emulsions. , 2009, Langmuir : the ACS journal of surfaces and colloids.

[5]  N. Cameron,et al.  Reversible Immobilization onto PEG‐based Emulsion‐templated Porous Polymers by Co‐assembly of Stimuli Responsive Polymers , 2009 .

[6]  Connie B. Chang,et al.  Nanoscale double emulsions stabilized by single-component block copolypeptides , 2008, Nature.

[7]  P. Rocha-Filho,et al.  W/O/W Multiple Emulsions Obtained by One‐Step Emulsification Method and Evaluation of the Involved Variables , 2008 .

[8]  Irena Pulko,et al.  Atrazine removal by covalent bonding to piperazine functionalized PolyHIPEs. , 2007, The Science of the total environment.

[9]  Chun-tian Zhao,et al.  Emulsion-templated porous materials (PolyHIPEs) for selective ion and molecular recognition and transport: applications in electrochemical sensing , 2007 .

[10]  J. V. Hest,et al.  Covalent Enzyme Immobilization onto Photopolymerized Highly Porous Monoliths , 2006 .

[11]  P. Krajnc,et al.  4-Vinylbenzyl chloride based porous spherical polymer supports derived from water-in-oil-in-water emulsions , 2005 .

[12]  R. Backov,et al.  Generation of Palladium Nanoparticles within Macrocellular Polymeric Supports: Application to Heterogeneous Catalysis of the Suzuki–Miyaura Coupling Reaction , 2005 .

[13]  J. Meuldijk,et al.  Electrosteric stability of styrene/acrylic acid copolymer latices under emulsion polymerization reaction conditions , 2005 .

[14]  J. Salager,et al.  Using emulsion inversion in industrial processes. , 2004, Advances in colloid and interface science.

[15]  N. Garti,et al.  Double emulsions stabilized with hybrids of natural polymers for entrapment and slow release of active matters. , 2004, Advances in colloid and interface science.

[16]  R. Mezzenga,et al.  Design of double emulsions by osmotic pressure tailoring. , 2004, Langmuir : the ACS journal of surfaces and colloids.

[17]  Dan S. Tawfik,et al.  In vitro compartmentalization by double emulsions: sorting and gene enrichment by fluorescence activated cell sorting. , 2004, Analytical biochemistry.

[18]  B. Brooks,et al.  Phase Inversion in Abnormal O/W/O Emulsions. 2. Effect of Surfactant Hydrophilic−Lipophilic Balance , 2003 .

[19]  Jae-Hyung Jang,et al.  Controllable delivery of non-viral DNA from porous scaffolds. , 2003, Journal of controlled release : official journal of the Controlled Release Society.

[20]  M. Kanouni,et al.  Preparation of a stable double emulsion (W1/O/W2): role of the interfacial films on the stability of the system. , 2002, Advances in colloid and interface science.

[21]  O. Mondain-Monval,et al.  Synthesis and functionalisation of polyHIPE® beads , 2002 .

[22]  A. Cooper,et al.  Synthesis of Monodisperse Emulsion-Templated Polymer Beads by Oil-in-Water-in-Oil (O/W/O) Sedimentation Polymerization , 2002 .

[23]  D. Burgess,et al.  Multiple emulsion stability: pressure balance and interfacial film strength. , 2002, Journal of colloid and interface science.

[24]  J. Salager,et al.  Effect of stirring energy upon the dynamic inversion hysteresis of emulsions , 2001 .

[25]  K. Papadopoulos,et al.  Effects of Surfactants on Water Transport in W1/O/W2 Emulsions , 2000 .

[26]  J. Salager,et al.  Current Phenomenological Know-How and Modeling of Emulsion Inversion , 2000 .

[27]  P. A. Reynolds,et al.  High Internal Phase Water-in-Oil Emulsions Studied by Small Angle Neutron Scattering , 2000 .

[28]  J. Engberts,et al.  Aggregation Behavior of Mono-endcapped Hydrophobically Modified Poly(sodium acrylate)s in Aqueous Solution. , 2000, Journal of colloid and interface science.

[29]  H. Rosano,et al.  Stability of W1/O/W2 multiple emulsions: Influence of ripening and interfacial interactions , 1998 .

[30]  N. Garti Double emulsions — scope, limitations and new achievements , 1997 .

[31]  H. N. Stein,et al.  Predicting Catastrophic Phase Inversion on the Basis of Droplet Coalescence Kinetics , 1996 .

[32]  H. N. Stein,et al.  The Applicability of Catastrophe Theory to Emulsion Phase Inversion , 1995 .

[33]  B. Binks Emulsion type below and above the CMC in AOT microemulsion systems , 1993 .

[34]  H. Schott,et al.  Shifts in the apparent ionization constant of the carboxylic acid groups of gelatin. , 1985, Journal of pharmaceutical sciences.

[35]  D. Cistola,et al.  The Ionization Behavior of Fatty Acids and Bile Acids in Micelles and Membranes , 1984, Hepatology.

[36]  S. Magdassi,et al.  Multiple emulsions II: HLB shift caused by emulsifier migration to external interface , 1984 .

[37]  S. Matsumoto Development of W/O/W-type dispersion during phase inversion of concentrated W/O emulsions , 1983 .

[38]  P. Gresham,et al.  Use of a Sustained-release Multiple Emulsion to Extend the Period of Radioprotection conferred by Cysteamine , 1971, Nature.

[39]  J. Salager,et al.  Emulsion catastrophic inversion from abnormal to normal morphology. 2. Effect of the stirring intensity on the dynamic inversion frontier , 2003 .

[40]  A. Barbetta,et al.  High internal phase emulsions (HIPEs) containing divinylbenzene and 4-vinylbenzyl chloride and the morphology of the resulting PolyHIPE materials , 2000 .