Preparation of Uniform-Sized Polystyrene−Polyacrylamide Composite Microspheres from a W/O/W Emulsion by Membrane Emulsification Technique and Subsequent Suspension Polymerization

Ma, Guanghui; Sone, Hideaki; Omi, Shinzo

doi:10.1021/ma035316g

Cited by 100 publications

(62 citation statements)

References 23 publications

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“…Ma et al [58] investigated the production of polystyrene-polyacrylamide Nagashima et al [59,123] attempted production of poly(acrylamide-co-acrylic acid)…”

Section: One-stage (Direct) Suspension Polymerisationmentioning

confidence: 99%

Recent developments in manufacturing emulsions and particulate products using membranes

Vladisavljević

Williams

2005

Advances in Colloid and Interface Science

325

196

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Membrane emulsification is a relatively new technique for the highly controlled production of particulates. This review focuses on the recent developments in this area, ranging from the production of simple oil-in-water (O/W) or water-in-oil (W/O) emulsions to multiple emulsions of different types, solid-in-oil-in-water (S/O/W) dispersions, coherent solids (silica particles, solid lipid microspheres, solder metal powder), and structured solids (solid lipid microcarriers, gel microbeads, polymeric microspheres, core-shell microcapsules and hollow polymeric microparticles). Other emerging technologies that extend the capabilities into different membrane materials and operation methods (such as rotating membranes, repeated membrane extrusion of coarsely pre-emulsified feeds) are introduced. The results of experimental work carried out by cited researchers in the field together with those of the current authors are presented in a tabular form in a rigorous and systematic manner. These demonstrate a wide range of products that can be manufactured using different membrane approaches. Opportunities for creation of new and novel entities are highlighted for low throughput applications (medical diagnostics, healthcare) and for large scale productions (consumer and personal products).

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“…Ma et al [58] investigated the production of polystyrene-polyacrylamide Nagashima et al [59,123] attempted production of poly(acrylamide-co-acrylic acid)…”

Section: One-stage (Direct) Suspension Polymerisationmentioning

confidence: 99%

Recent developments in manufacturing emulsions and particulate products using membranes

Vladisavljević

Williams

2005

Advances in Colloid and Interface Science

325

196

View full text Add to dashboard Cite

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mentioning

confidence: 99%

“…Several examples of the copolymerization of the partially water-soluble monomer acrylamide (AAm) and oil-soluble monomers such as methacrylic acid 26 and styrene 27,28 have been recently reported with precipitation polymerization, 26 inverse microemulsion polymerization, 27 and water/oil/water emulsion by SPG membrane emulsification and subsequent suspension polymerization. 28 In our previous studies, poly(St-co-DVB) and poly (MMA-co-DVB) microspheres containing various concentrations of divinylbenzene (DVB), from 5 to 75 mol %, were synthesized by precipitation polymerization, and their unexpected thermal properties, superior to those of crosslinked polymers prepared by emulsion and suspension polymerization, were found to be due to a fully crosslinked microstructure.…”

mentioning

confidence: 99%

Synthesis of poly(acrylamide‐co‐divinylbenzene) microspheres by precipitation polymerization

Jin

Yang

Shim

et al. 2005

J. Polym. Sci. A Polym. Chem.

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The synthesis and application of polymeric microspheres are of great importance from both academic and industrial points of view. As polymeric microspheres have been used in wider fields of conventional 1 and more sophisticated 2-6 areas, the development of a new process to prepare such materials has received much attention. Polymer microspheres of a particular size and uniformity are generally obtained with one of the heterogeneous polymerizations, including suspension, emulsion, dispersion, seeded, and precipitation polymerizations. Moreover, each polymerization is branched to several subsidiary methods, such as macroemulsion, miniemulsion, microemulsion, and soap-free emulsion polymerizations.Fully crosslinked monodisperse polymer microspheres have unique applications because of their superior strength, thermal and solvent resistance, and antislip properties.7 However, the synthesis of such microspheres is limited to a few techniques, such as seeded polymerization, [8][9][10][11] Shirasu porous glass (SPG) membrane emulsification followed by postpolymerization, 12,13 and precipitation polymerization.14 Precipitation polymerization, in particular, has advantages over the other techniques because crosslinked microspheres can be readily prepared in a single process without any auxiliary apparatus to make the size distribution of the particles narrow. Therefore, homoand copolymerization systems have been thoroughly investigated, including poly(divinylbenzene), 15 poly (methacrylic acid-co-polyethylene oxide methyl ether methacrylate), 16 poly(methacrylate-co-divinylbenzene), 17 poly(chloromethylstyrene-co-divinylbenzene), 18 poly(divinylbenzene-co-maleic anhydride) 19 , poly(methyl methacrylate-co-divinylbenzene)[poly(MMA-co-DVB)], [20][21][22] and poly(styrene-co-divinylbenzene) [poly(St-co-DVB)]. 23In addition, mechanistic studies to elucidate the formation of stable microspheres in the absence of any stabilizer have been reported 24,25 in which the absorption of oligomeric species onto the nuclei and the high degree of crosslinking are the primary reasons for the formation and stable growth of the microspheres.Several examples of the copolymerization of the partially water-soluble monomer acrylamide (AAm) and oil-soluble monomers such as methacrylic acid 26 and styrene 27,28 have been recently reported with precipitation polymerization, 26 inverse microemulsion polymerization, 27 and water/oil/water emulsion by SPG membrane emulsification and subsequent suspension polymerization. 28In our previous studies, poly(St-co-DVB) and poly (MMA-co-DVB) microspheres containing various concentrations of divinylbenzene (DVB), from 5 to 75 mol %, were synthesized by precipitation polymerization, and their unexpected thermal properties, superior to those of crosslinked polymers prepared by emulsion and

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“…The MEsuspension polymerisation (MESP) method was used to prepare polymer particles with tuneable size, shape, internal morphology, and porosity (Omi et al, 1994). Suspension polymerisation was performed within O/W , W/O (Hu et al, 2011) or W/O/W emulsion prepared by ME (Ma et al, 2004) and was combined with droplet swelling method to synthesise particles from hydrophilic monomers (Omi et al, 1997;Vladisavljević and Williams, 2005).…”

Section: Integration Of Membrane Emulsification and Suspension Polymementioning

confidence: 99%

Structured microparticles with tailored properties produced by membrane emulsification

Vladisavljević

2015

Advances in Colloid and Interface Science

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This paper provides an overview of membrane emulsification routes for fabrication of structured microparticles with tailored properties for specific applications. Direct (bottom-up) and premix (top-down) membrane emulsification processes are discussed including operational, formulation and membrane factors that control the droplet size and droplet generation regimes. A special emphasis was put on different methods of controlled shear generation on membrane surface, such as cross flow on the membrane surface, swirl flow, forward and backward flow pulsations in the continuous phase and membrane oscillations and rotations. Droplets produced by membrane emulsification can be used for synthesis of particles with versatile morphology (solid and hollow, matrix and core/shell, spherical and non-spherical, porous and coherent, composite and homogeneous), which can be surface functionalised and coated or loaded with macromolecules, nanoparticles, quantum dots, drugs, phase change materials and high molecular weight gases to achieve controlled/targeted drug release and impart special optical, chemical, electrical, acoustic, thermal and magnetic properties. The template emulsions including metal-in-oil, solid-in-oil-in-water, oil-in-oil, multilayer, and Pickering emulsions can be produced with high encapsulation efficiency of encapsulated materials and narrow size distribution and transformed into structured particles using a variety of different processes, such as polymerisation (suspension, mini-emulsion, interfacial and in-situ), ionic gelation, chemical crosslinking, melt solidification, internal phase separation, layer-by-layer electrostatic deposition, particle self-assembly, complex coacervation, spray drying, sol-gel processing, and molecular imprinting. Particles fabricated from droplets produced by membrane emulsification include nanoclusters, colloidosomes, carbon aerogel particles, nanoshells, polymeric (molecularly imprinted, hypercrosslinked, Janus and core/shell) particles, solder metal powders and inorganic particles. Membrane 2 emulsification devices operate under constant temperature due to low shear rates on the membrane surface, which range from (1−10) × 10 3 s −1 in a direct process to (1−10) × 10 4 s −1 in a premix process.Keywords: Membrane Emulsification; Polymeric microsphere; Microgel; Janus Particle; Core/Shell Particle, Colloidosome. Membrane emulsificationMembrane emulsification (ME) involves preparation of emulsions by pressing a pure dispersed phase or pre-emulsified mixture of the dispersed and continuous phase through a microporous membrane under controlled injection rate and shear conditions. In direct membrane emulsification (DME), one liquid (a dispersed phase) is injected through a microporous membrane into another immiscible liquid (the continuous phase) (Nakashima et al., 1991;, which leads to the formation of droplets at the membrane/continuous phase interface ( Figure 1a). In premix membrane emulsification (PME) (Figure 1b), a pre-emulsion is pressed through the membrane (...

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Preparation of Uniform-Sized Polystyrene−Polyacrylamide Composite Microspheres from a W/O/W Emulsion by Membrane Emulsification Technique and Subsequent Suspension Polymerization

Cited by 100 publications

References 23 publications

Recent developments in manufacturing emulsions and particulate products using membranes

Recent developments in manufacturing emulsions and particulate products using membranes

Synthesis of poly(acrylamide‐co‐divinylbenzene) microspheres by precipitation polymerization

Structured microparticles with tailored properties produced by membrane emulsification

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