粒子与聚合物协同稳定高内相Pickering乳液

选用二氧化硅纳米粒子(H30)和聚(乳酸-羟基乙酸)共聚物(PLGA)为复合稳定剂, 成功制备出内相体积分数高达90%的高内相Pickering 乳液. 对照实验表明: 单独用H30粒子作稳定剂, 内相体积分数上限为75%; 单独用PLGA 作稳定剂, 发生严重相分离, 不能形成乳液. 无机纳米粒子与聚合物之间的协同作用在制备高内相乳液的过程中起到了关键作用. 因此, 使用无机粒子和聚合物作为混合稳定剂制备高内相乳液是一种新型而有效的方法.     

Synthesis of star polymeric ionic liquids and use as the stabilizers for high internal phase emulsions

A series of well-defined core cross-linked star (CCS) polymeric ionic liquids (PILs) were synthesized via a three-step approach. First, the styrenic imidazole-based CCS polymer (S-PVBnIm) was prepared by the RAFT-mediated heterogeneous polymerization in a water/ethanol solution, followed by the quaternization of S-PVBnIm with bromoalkanes and anion exchange. The CCS polymers were characterized by gel permeation chromatography (GPC), nuclear magnetic resonance (NMR) spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermal gravimetric analysis (TGA), and differential scanning calorimetry (DSC). The obtained CCS polymers were used as the effective emulsifiers for oil-in-water high internal phase emulsions (HIPEs). Multiple oils with different polarity including n-dodecane, undecanol, toluene and octanol were emulsified using 0.5 wt% S-PVBnIm aqueous solution under the acidic condition to form HIPEs with long-term stabilities. The excellent emulsification properties of CCS PILs were demonstrated by HIPE formation for a variety of oils. The properties of HIPEs in terms of emulsion type and oil droplet size were characterized by the confocal laser scanning microscopy (CLSM). The intriguing capability of CCS PILs to stabilize HIPEs of various oils holds great potentials for the practical applications.     

Preparation of Surface-Imprinted Polymer Magnetic Nanoparticles with Miniemulsion Polymerization for Recognition of Salicylic Acid

Molecular surface-imprinted polymers nanoparticles encapsulating magnetite modified with oleic acid, for recognition of salicylic acid was prepared by three-step miniemulsion polymerization. The important factors including polymerization process, solvents, miniemulsifying approaches, and co-stabilizer have been investigated to obtain magnetic molecular imprinting polymers (MMIPs) nanoparticles (NPs) with high saturation magnetization (Ms), regular morphology, and good monodispersion. The results showed that the amount of magnetite encapsulated in MMIPs NPs was 43.4 wt% and Ms was 33.584 emu/g. Thus, MMIPs NPs could be separated easily within 2 minutes by an external magnetic field. The transmission electron microscope (TEM) showed MMIPs NPs were of regular sphere with core-shell structure, where magnetite NPs were uniformly encapsulated in homogeneous polymer shells. The average diameter of MMIPs NPs was 98 nm with RSD of 6.6%. Good recognition and high loading of target molecule were achieved by MMIPs NPs in batch rebinding tests.     

Macroporous Polymers with Hierarchical Pore Structure from Emulsion Templates Stabilised by Both Particles and Surfactants

Inspired by natural porous materials, such as wood, bamboo and spongy bone consisting of individual structural units that are hierarchically arranged to optimise mechanical properties such as strength and toughness, synthetic macroporous polymers with enhanced physical properties were created by emulsion templating. Hierarchical poly(merised) high internal phase emulsions (HIPE) were created from HIPEs stabilised simultaneously by particles and a surfactant. In these HIPEs, surfactant stabilised and particle stabilised water droplets coexist, which upon polymerisation of the minority oil phase gives rise to macroporous polymers with a hierarchical pore structure. An improvement of the mechanical properties of our hierarchically structured macroporous polymers at equal porosity was observed, due to a more efficient packing of pores in a configuration that improves mechanical strength despite the presence of interconnecting pore throats. Moreover, the permeability of the hierarchically structured polyHIPEs are exceeding those measured for conventional polyHIPEs made from surfactant only stabilised HIPEs.

     

Pure Protein Scaffolds from Pickering High Internal Phase Emulsion Template

The formation of hierarchical porous protein scaffolds from oil‐in‐water (o/w) high internal phase emulsions (HIPEs) stabilized by bovine serum albumin (BSA) protein nanoparticles (Pickering HIPE) is reported. The route consists of three principal steps. First, a stable o/w HIPE stabilized by BSA protein nanoparticles is formulated. Next, crosslinking the dispersed protein nanoparticles gives rise to a gel in the continuous water phase to freeze the emulsion's microstructure. Finally, removal of the oil components and water directly leads to a three dimensional, bimodal meso‐macroporous protein scaffold, which is suitable for a wide range of biomedical applications.     

Hydrophilic polymer foams with well‐defined open‐cell structure prepared from pickering high internal phase emulsions

Open‐cell hydrophilic polymer foams are prepared through oil‐in‐water Pickering high internal phase emulsions (HIPEs). The Pickering HIPEs are stabilized by commercial titania (TiO₂) nanoparticles with adding small amounts of non‐ionic surfactant Tween85. The morphologies, such as average void diameter and interconnectivity, of the foams can be tailored easily by varying the TiO₂ nanoparticles and Tween85 concentrations. Further, investigation of the HIPE stability, emulsion structure and the location of TiO₂ nanoparticles in resulting foams shows that the surfactant tends to occupy the oil‐water interface at the contact point of adjacent droplets, where the interconnecting pores are hence likely to be formed after the consolidation of the continuous phase. © 2013 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2013     

Tough interconnected polymerized medium and high internal phase emulsions reinforced by silica particles

Emulsion templating using high internal phase emulsions is an effective route to prepare low density and high porosity macroporous polymers known as polymerized high internal phase emulsions (polyHIPEs). Conventional polyHIPEs, synthesized from surfactant stabilized w/o emulsions have low permeabilities and poor mechanical properties. We present interconnected open macroporous low density nanocomposites produced by polymerizing the continuous phase of emulsion templates, which contained styrene, polyethyleneglycoldimethacrylate, and silylated silica particles. Polyethyleneglycoldimethacrylate and the silylated silica particles acted as crosslinker. The functionalized silica particles were incorporated into the polymer, which resulted in a significant improvement of the mechanical properties of the polyHIPEs without affecting the interconnected and permeable pore structures. The polyHIPEs contained up to 60 wt % silylated silica particles. Young's modulus of the reinforced macroporous polymers increased up to 600% compared with nonreinforced macroporous polymers. The mechanical performance was further increased by increasing the foam density of the macroporous nanocomposites from around 200 to 370 g/cm³ by raising the organic phase volume of the emulsion templates from 20 to 40 vol %. The macroporous polymers synthesized from less concentrated emulsions also possessed interconnected open porous although less permeable structures. The polyHIPE nanocomposites have a permeability of about 200 mD, whereas the polyMIPE nanocomposites still have permeabilities of around 50 mD. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 1979–1989, 2010     

Aryl acrylate based high‐internal‐phase emulsions as precursors for reactive monolithic polymer supports

Water‐in‐oil high‐internal‐phase emulsions (HIPEs), containing 4‐nitrophenyl acrylate and 2,4,6‐trichlorophenyl acrylate as reactive monomers, were prepared and polymerized, and highly porous monolithic materials resulted. The novel materials were studied by combustion analysis, Fourier transform infrared spectroscopy scanning electron microscopy, mercury porosimetry, and N₂ adsorption/desorption analysis. With both esters, cellular macroporous monolithic polymers were obtained; the use of 4‐nitrophenyl acrylate resulted in a cellular material with void diameters between 3 and 7 μm and approximately 3‐μm interconnects, whereas the use of 2,4,6‐trichlorophenyl acrylate yielded a foam with void diameters between 2 and 5 μm, most interconnects being around 1 μm. The resulting monoliths proved to be very reactive toward nucleophiles, and possibilities of functionalizing the novel polymer supports were demonstrated via reactions with amines bearing additional functional groups and via the synthesis of an acid chloride derivative. Tris(hydroxymethyl)aminomethane and tris(2‐aminoethyl)amine derivatives were obtained. The hydrolysis of 4‐nitrophenylacrylate removed the nitrophenyl group, yielding a monolithic acrylic acid polymer. Furthermore, functionalization to immobilized acid chloride was performed very efficiently, with more than 95% of the acid groups reacting. The measurement of the nitrogen content in 4‐nitrophenyl acrylate poly(HIPE)s after various times of hydrolysis showed the influence of the total pore volume of the monolithic polymers on the velocity of the reaction, which was faster with the more porous polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 296–303, 2005     

Fabrication of a composite colloidal particle with unusual janus structure as a high-performance solid emulsifier

Core-shell particles with cross-linked core and shell were used as seed particles to produce composite Janus particles. It was found that when the shell has distinctly higher cross-linking degree than the core, Janus particles with very unusual structures can be obtained. These particles have two parts, with one part embraced partially or entirely by the other part, adjustable by parameters such as phase ratio or cross-linking degree. On the basis of experimental observations, a possible mechanism for the formation of such unusual Janus particles has been proposed. Janus particles with arms are used to emulsify water-toluene mixtures, forming oil-in-water (O/W) emulsions at very high internal phase content with rather low concentration of particles. Nonspherical emulsion droplets were observed, indicating that these Janus particles are likely to jam at the interface, forming a strong protecting layer to stabilize emulsions.     

Fabrication of macroporous foam and microspheres of polystyrene by Pickering emulsion polymerization

Poly(styrene-co-methacrylic acid) (PS-co-MAA) particles were synthesized via surfactant-free emulsion polymerization and then used as particulate emulsifiers for preparation of Pickering emulsions. Our results showed that adjusting the solution pH can tune the wettability of PS-co-MAA particles to stabilize either water-in-oil (W/O) or oil-in-water (O/W) Pickering emulsions. Stable W/O emulsions were obtained with PS-co-MAA particles at low pH values due to their better affinity to the dispersed oil phase. In contrast, increasing the pH value significantly changed the stabilizing behavior of the PS-co-MAA particles, leading to the phase inversion and formation of stable O/W emulsions. We found that the oil/water ratio had a significant influence on pH value of the phase inversion. It decreased with decreasing the oil/water ratio, and no phase inversion occurred when the styrene volume fraction reduced to 10 %. Additionally, macroporous polystyrene (PS) foam and PS microspheres were obtained via polymerization of Pickering high internal phase emulsion (Pickering HIPE) and O/W Pickering emulsion, respectively.     

Carbon nanotubes in emulsion‐templated porous polymers: Polymer nanoparticles,sulfonation, and conductivity

Sulfonated polymers are of interest for ion exchange resins, reaction supports, and membranes for separation, filtration, fuel cells, and electrochemical devices. Sulfonic groups have been introduced into polystyrene (PS) through exposure to sulfuric acid, and carbon nanotubes (CNTs) have been added to polymers to enhance proton conductivity without creating an electronic percolation pathway. PolyHIPEs, emulsion‐templated porous polymers with highly interconnected hierarchical open‐cell porous structures, are synthesized through polymerization in the external phases of high internal phase emulsions (HIPEs). In this article, the synthesis of PS‐based CNT‐filled polyHIPEs, their structure, sulfonation, and conductivity are described. Adding CNT dispersions to the HIPEs produced polymer nanoparticle–covered polyHIPEs from polymerization within the water‐soluble surfactant micelles in the internal aqueous phase droplets. The CNTs migrated from the HIPE's aqueous phase droplets into the HIPE's organic phase and formed interconnected bundles within the polyHIPE walls, reflecting a reduction in the surfactant's ability to disperse the CNTs. The water adsorption in the hygroscopic sulfonated polyHIPEs increased the conductivity by several orders of magnitude. The conductivity of the sulfonated polyHIPE containing CNTs was more than an order of magnitude greater than that of the sulfonated polyHIPEs with no CNTs. The CNTs act as “bridges,” enhancing the connection between existing conductive pathways. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4369–4377     

Rheology of high internal phase emulsions

The mechanical dispersion technology used in this study employs rotor-stator mixers that produce water-continuous high internal phase emulsions (HIPEs) with narrow drop size distributions and small drop sizes, even when the internal phase (oil) viscosity is quite high. Analysis of these HIPEs reveals trends that are consistent with formation by a capillary instability mechanism in which a shear deformation produces highly elongated drops that rupture to form uniform, small droplets. In the search for a predictive tool to aid in the manufacture and use of HIPEs, rheology data for these shear-thinning HIPEs have been compared to data for models in the literature. Existing models do not correctly account for the effect of a high internal phase viscosity on the rheological properties of the HIPE. Another shortcoming is failure to correctly address the shear-thinning exponent. Whereas internal phase viscosity does not seem to affect the shear-thinning exponent, the surfactant apparently plays an important role, possibly through its modification of the interfacial tension and continuous phase rheology.     

Thermoresponsive Macroporous Scaffolds Prepared by Emulsion Templating

A versatile method to prepare non‐covalently crosslinked polyHIPEs hydrogels from oil‐in‐water high internal phase emulsions (HIPEs) whose aqueous phase contained thermo‐responsive linear polymers is described. The interconnected pore structure of the polyHIPEs is maintained by reversible physical aggregation of thermo‐responsive polymer chains in an aqueous environment. This method to prepare interconnected porous hydrogels using a thermal trigger in the guise of thermo‐responsive polymers by emulsion templating requires no chemical reaction during solidification of the template. This particular feature could provide a safer route to injectable scaffolds as issues of polymerisation/crosslinking chemistry and residual initiator fragments or monomers do not arise     

烷基胺作为络合剂制备亲油性纳米银

在烷基胺/油酸/水混合体系中制备出表面包裹的亲油性纳米银颗粒,体系中的烷基胺作为络合剂和稳定剂起到使Ag离子水溶液与油酸互溶的作用,在还原过程中均匀释放出Ag离子,使Ag表面被油酸包裹具有亲油性。在相同反应条件下,分别以环己胺、正丁胺、三乙胺作为络合剂,考察了不同结构的胺对纳米Ag的形成过程以及对纳米Ag的表面性质和形貌的影响,并考察了所得纳米Ag颗粒的热稳定性。结果表明,相同反应条件下,正丁胺和三乙胺比环己胺更适于作为络合剂和稳定剂来制备油酸包裹的亲油性纳米Ag,所制备的纳米Ag颗粒在烷烃等中具有较好的热稳定性。     

Synthesis and Catalytic Performance of Hierarchically Porous MIL‐100(Fe)@polyHIPE Hybrid Membranes

Metal‐organic frameworks (MOFs) nanoparticles in combination with a nonionic surfactant (Pluronic L‐121) are used to stabilize dicyclopentadiene (DCPD)‐in‐water high internal phase emulsions (HIPEs). The resulting HIPEs containing the MIL‐100(Fe) nanoparticles (MIL: Materials of Institut Lavoisier) at the interface between the oil‐ and the water‐phases are then cured, and 100 μm thick, fully open, hierarchically porous hybrid membranes are obtained. The properties of the MIL‐100(Fe)@pDCPD polyHIPE membranes are characterized and it is found that up to 14 wt% of the MIL‐100(Fe) nanoparticles are incorporated in the hybrid material resulting in an increase of the microporosity up to 130 m² g⁻¹. Hybrid membranes show an appealing catalytic activity in Friedel–Crafts alkylation in a batch mode as well as in a flow‐through mode, thereby demonstrating the preserved accessibility of Lewis acidic sites in the MOF nanostructures.

     

Oil-in-alcohol highly concentrated emulsions as templates for the preparation of macroporous materials

New oil-in-alcohol highly concentrated emulsions were formulated and were used as a templates to obtain macroporous poly(furfuryl alcohol) monoliths by a one-step method. The oil-in-alcohol highly concentrated emulsions were prepared by stepwise addition of the oil phase to the surfactant-alcohol solution and were characterized by optical microscopy and by laser diffraction. The typical structure of highly concentrated emulsions, with close-packed polyhedral droplets, has been observed. Poly(furfuryl alcohol) monoliths were obtained by polymerizing in the external phase of these emulsions. These materials are mainly macroporous and retain the size distribution and morphology from the highly concentrated emulsions. The internal structure of the monoliths was observed by scanning electron microscopy. The images showed an interconnected network with pore size similar to the droplet size of the highly concentrated emulsions used as templates.     

Fabrication of novel multihollow superparamagnetic magnetite/polystyrene nanocomposite microspheres via water-in-oil-in-water double emulsions

We herein present a novel and simple synthetic strategy for fabricating multihollow superparamagnetic magnetite/polystyrene nanocomposite microspheres via water-in-oil-in-water double emulsions. Amphipathic magnetite nanoparticles surface-modified with oleic acid act as an oil-soluble emulsifier and sodium dodecyl sulfate acts as a water-soluble surfactant in the system. The final products were thoroughly characterized by X-ray powder diffraction, Fourier transform infrared spectroscopy, transmission electron microscopy, and field-emission scanning electron microscopy, which showed the formation of multihollow magnetite/polystyrene nanocomposite microspheres. Preliminary results of magnetic properties of multihollow magnetite/polystyrene microspheres were reported. The effect of the content of amphipathic magnetite nanoparticles on the morphology of nanocomposite microspheres was studied. Furthermore, the mechanism of formation of multihollow magnetic nanocomposite microspheres was also discussed.     

Hydrophobin coated boehmite nanoparticles stabilizing oil in water emulsions

Hydrophobin coated boehmite nanoparticles have been used to establish tooth-paste like, homogenous emulsions. The surface-modified nanoparticles were simply obtained by mixing aqueous solutions of cationic boehmite particles with the anionic hydrophobin H Star Protein B® (HPB). Surface tension measurements clearly show that 1 wt.% boehmite binds up to 1 wt.% HPB. The strong interaction and aggregation of hydrophobin coated boehmite nanoparticles was proven by Cryo-TEM measurements, too. Interestingly, the combined use of 0.5 wt.% HPB and 0.5 wt.% boehmite as emulsifying agents resulted in very stable, homogenous, high internal phase emulsions (65 wt.% oil) that are stable over months. The established emulsions have also been characterized by rheological measurements. Storage moduli of more than 1000 Pa are characteristic for their high gel-like properties. Furthermore, light microscopy showed an average droplet size close to 1 μm with low polydispersity. Cryo-SEM confirmed that the hydrophobin coated nanoparticles are located at the interface of the oil droplets and therefore stabilize the emulsion systems.     

高内相比乳液模板法合成多孔材料的研究进展

综述了以高内相比乳液作模板制备多孔材料的研究进展,介绍了油包水(W/O)乳液体系法、水包油(O/W)乳液体系法和超临界CO2法等制备方法、各种多孔材料的泡孔及通道直径、比表面积、密度等性能,以及这类多孔材料在生物医学、有机化学品清除、化学催化、水溶液中固体杂质分离、液相色谱、电化学传感器等领域的应用,并对其发展前景进行了展望。     

Di-block copolymer stabilized methyl methacrylate based polyHIPEs: Influence of hydrophilic and hydrophobic co-monomers on morphology,wettability and thermal properties

Due to intermediate hydrophobicity of methyl methacrylate (MMA) monomer in water, it is difficult to prepare its stable water in oil high internal phase emulsion (HIPE). Moreover, the addition of fully hydrophilic co-monomer such as 2-hydroxyethyl methacrylate (HEMA) in MMA monomer makes it further troublesome to stabilize these emulsions. This paper addresses the preparation of such type of difficult to prepare emulsions via addition of an amphiphilic fluorinated di-block copolymer (FDB), poly(2-dimethylamino)ethylmethacrylate-b-poly(trifluoroethyl methacrylate) (PDMAEMA-b-PTFEMA) as stabilizer. Interestingly, HEMA and/or HFBA (hexa fluorobutyl acrylate) as co-monomers were successfully added to impart some special properties such as thermodynamic stability, desired amphiphilicity to the final polyHIPEs. Fluorinated blocks in FDB anchored well at oil/water interface of HIPE, offering enough hydrophobicity to the comparatively hydrophilic monomers and in turn providing resistance against coalescence. MMA polyHIPEs were found to be fully hydrophobic just by replacing HEMA co-monomer with HFBA. Due to superb inherent hydrophobic nature of fluorine atoms, MMA-HFBA polyHIPEs showed remarkable water contact angle of 139°. Furthermore, the addition of fluorinated co-monomer in MMA based HIPEs significantly improved thermal stabilities of these materials with improvement in degradation temperature from 305 °C to 360 °C.