Synthesis of monodisperse porous poly(divinylbenzene) microspheres by distillation-precipitation polymerization

Highly crosslinked monodisperse porous poly(divinylbenzene) (PDVB) microspheres were prepared by distillation-precipitation polymerization in acetonitrile containing up to 25 vol% of toluene as porogen with 2,2′-azobisisobutyronitrile (AIBN) as initiator in the absence of any stabilizer or surfactant. The porous polymer microspheres were formed through a precipitation manner during the distillation of the solvent from the reaction system. Monodisperse porous polymer particles with spherical shape and smooth surface were synthesized with diameters in the range of 1.86 and 3.06 μm, total porosity of up to 0.30 cm³/g and specific surface area as high as 762 m²/g. The growth procedure of porous PDVB microsphere was characterized by SEM technique for morphological observation and isotherm nitrogen adsorption for the determination of the special surface area and porosity. The resultant porous polymer microspheres had a novel structure with the gradual increasing of pore volume during distillation of the solvent out of the reaction system.     

Production of micron-sized hollow microspheres by suspension polymerization of St-DEGDA (diethylene glycol diacrylate) with petroleum ether (90-120 °C)

Suspension polymerization for the droplets of the mixture with monomers, solvent, initiator in water phase with a dispersant PVA was carried out. During the polymerization the molecular weight increasing resulted in the phase separation in the droplets, and a hollow structure was formed. The influence of the hollow structure of the content of the crosslinking agent (DEGDA) and the solvent was discussed. The hollow microspheres prepared in the present study were characterized by optical microscopy (OM), scanning electron microscopy (SEM), particle size analyzer and differential scanning calorimeter (DSC).     

Extraction of aminoglycoside antibiotics with reverse micelles

The reverse micelle system of sodium di-2-ethylhexyl phosphate was used to extract aminoglycoside antibiotics, neomycin and gentamicin. The aminoglycosides can be efficiently extracted into a reverse micelle solution, and the antibiotics extracted into the micelle phase can readily be recovered back to a divalent cation aqueous solution, such as Ca²⁺. The transfer efficiency, %E, is heavily dependent on pH and salt concentration in the aqueous feed solution. %E decreases drastically with pH in the pH range 8·5–11, and declines with increasing (NH₄)₂SO₄ concentration. A simple transfer mechanism was proposed which suggests that the antibiotic molecules were extracted into the inner water cores of reverse micelles through attractive electrostatic interaction during forward transfer. In backward transfer, the antibiotics loaded in the micelle phase are released back to an aqueous phase through breaking up of the reverse micelles by using divalent cation solutions. The model is supported by the results of dynamic light scattering and infra-red spectroscopy study.     

Monodisperse macroporous poly(glycidyl methacrylate) microspheres coated with silica: Design,preparation and characterization

Monosized macroporous poly(glycidyl methacrylate) (PGMA) microspheres that were 9.3 μm in size were synthesized by multistep swelling polymerization using a modified Ugelstad technique. The PGMA microspheres and their hydrolyzed analogs derived from poly(2,3-dihydroxypropyl methacrylate) (PDHPMA) were coated by silanization with tetraethoxysilane (TEOS) and (3-aminopropyl)triethoxysilane (APTES), respectively. The particles were characterized by elemental and thermogravimetric (TGA) analysis, scanning and transmission electron microscopy (SEM and TEM) coupled with an energy dispersive X-ray analysis (EDAX) and FT-IR spectroscopy to determine the SiO₂ content, morphology, particle size, polydispersity and structure. These types of particles are expected to have improved biocompatibility relative to their starting polymers.     

Synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid

Poly(styrene‐co‐divinylbenzene) microspheres with size ranging from 1.6 to 1.8 μm were prepared in acetic acid by precipitation polymerization. The particle size and particle size distribution were determined by laser diffraction particle size analyzer, and the morphology of the particles was observed with scanning electron microscope. Besides, effects of various polymerization parameters such as initiator and total monomer concentration, divinylbenzene (DVB) content, polymerization time and polymerization temperature on the morphology and particle size were investigated in this article. In addition, the yield of microspheres increased with the increasing total monomer concentration, initiator loading, DVB concentration and polymerization time. In addition, the optimum polymerization conditions for synthesis of monodisperse crosslinked poly(styrene‐co‐divinylbenzene) microspheres by precipitation polymerization in acetic acid were obtained. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

The synthesis of nonporous poly(isobutyl methacrylate) microspheres by suspension polymerization technique and investigation of their swelling properties

Poly(isobutyl methacrylate) (PiBMA) microspheres with different crosslinking densities were synthesized by suspension polymerization technique in aqueous medium and their characterization and swelling behaviors in different solvents were investigated. PiBMA spheres with a 800‐ to 1500‐μm‐diameter range were obtained by using benzoyl peroxide (BPO) as polymerization initiator, 1/5 ratio of monomer/water in volume, tricalcium phosphate (TCP), and poly(N vinyl‐2‐pyrrolidone) (PVP) as suspension stabilizer with 350 rpm stirring rate in nitrogen atmosphere. The influence of type and amount of crosslinking agent on the swelling properties and diffusional behavior, diffusion coefficient, and network properties of the spheres were examined in pentane, hexane, heptane, and gasoline. Dynamic swelling behaviors of crosslinked spheres were determined by measuring the diameter of the sphere as a function of time by an optical microscope. Swelling behaviors and network properties were found to be dependent on the diameter, crosslinking density of the sphere, and crosslinking agent and solvent. The results of this study indicate that the crosslinked PiBMA microsphere can be swollen in gasoline very well and retains a high ratio (1500% of its volume) of gasoline in their structure. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 83: 349–356, 2002     

Preparation of poly(vinyl acetate) microspheres with narrow particle size distributions by low temperature suspension polymerization of vinyl acetate

To estimate influences of suspension polymerization conditions including conversion, polymerization temperature, stirring rate, initiator concentration, monomer concentration, and suspending agent concentration on the volume average diameter (D_avg) and particle size distribution (PSD) of poly(vinyl acetate) (PVAc) microspheres, vinyl acetate (VAc) was suspension‐polymerized at low temperature using 2,2′‐azobis(2,4‐dimethylvaleronitrile) as an initiator. The effects of each condition, on D_avg of PVAc microspheres, were expressed as follows, D_avg = [conversion]^a[temperature]^b[rpm]^c[ADMVN]^d[VAc]^f [suspending agent]^g. Logarithms of D_avg were linearly proportional to those of polymerization conditions, and their exponents, a, b, c, d, f, and g were calculated as 0.27, ?13.7, ?1.37, ?0.21, 0.58, and 0.29, respectively. Variations of PSDs, according to polymerization conditions, were examined by considering polymerization rate, droplet or suspension viscosity, and droplet break‐up/coagulation equilibrium. From these results, PVAc microspheres with various sizes and narrow PSDs were obtained effectively under carefully controlled polymerization conditions, which can be used as promising precursors of novel PVA microspheres through heterogeneous surface saponification. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4064–4070, 2006     

Synthesis,characterization, and swelling behavior of poly(N-hydroxymethylacrylamide) grafted poly(vinyl alcohol)

In this study, the graft copolymerization of N-hydroxymethylacrylamide (NHMAAm) with poly(vinyl alcohol) (PVA) was carried out by using potassium persulfate/N,N,N,N-tetramethylethylenediamine (K₂S₂O₈) to improve physicochemical properties and functionality of PVA. The structures of PVA-g-poly-NHMAAm (PNHMAAm) copolymers were characterized by Fourier transform infrared, elemental analysis, nuclear magnetic resonance (¹H-NMR), ¹³C-NMR, and size exclusion chromatography. Their thermal behaviors were investigated by differential scanning calorimetry and thermogravimetric analysis (TGA). The TGA results indicated that the graft copolymers show better thermal stability then PVA. The effects of reaction time, temperature, NHMAAm, and K₂S₂O₈ concentrations on grafting parameters were examined. The maximum grafting yield (34.01%) was provided when reaction was carried out under optimum conditions (time = 2 hr, T = 40°C, [NHMAAm] = 0.25 M, [K₂S₂O₈] = 4.56 × 10⁻³ M). Moreover, PVA-g-PNHMAAm membranes were prepared and their swelling behaviors were studied. The results demonstrated that swelling degree of graft membranes increased almost 3.5-fold compared to PVA membrane.     

碱溶胀法制备核壳中空微球研究进展

综述了碱溶胀法合成核壳中空微球的国内外研究进展,重点介绍了核壳中空结构的合成以及各种因素如聚合物组成,碱处理条件、乳化剂用量、单体瞬时转化率以及玻璃化温度对微球形态的影响。     

Synthesis of amphiphilic microspheres by suspension copolymerization of styrene and poly(ethylene oxide) macromonomer

Amphiphilic microspheres, ranging in size from 3 to 35 μm, were prepared by suspension copolymerization of styrene with poly(ethylene oxide) vinylbenzyl (PEO–VB) macromonomer by changing polymerization conditions. It was found that an increase in the amount of dispersant and the PEO–VB concentration resulted in decreases of the size and size distribution of amphiphilic microspheres. The morphology, size, and size distribution of amphiphilic microspheres were characterized by scanning electron microscopy. The structure of copolymer was confirmed by infrared spectroscopy, differential scanning calorimetry, elemental analysis, and X‐ray photoelectron spectroscopy. The content of the hydroxyl groups localized in the microspheres ranged from 0.05 to 0.2 mmol/g. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 333–339, 2001     

A comprehensive study of extraction of hyperoside from Hypericum perforatum L. using CTAB reverse micelles

BACKGROUND: Hyperoside is a valuable natural pharmaceutical that has many biomedical functions. By the traditional method of alcohol extraction, only hyperoside solution of very low concentration can be obtained, so a new method is urgently needed to produce pure hyperoside more effectively. Reverse micellar extraction has been widely used in the purification of biological macromolecules. Theoretically, this method could also be used to purify materials with small molecules. Therefore it would seem appropriate to consider the extraction of hyperoside, a material with small molecules, using reverse micelles. In this study the factors affecting hyperoside extraction using cetyl trimethylammonium bromide (CTAB) reverse micelles were comprehensively investigated. RESULTS: The results showed that the partition coefficient increases with an increase in aqueous phase pH or CTAB concentration before reaching a saturated state. The existence of anions in the system can affect the extraction in several ways. For example, SO and PO ions can form hydrogen bonds with hyperoside and thereby improve the extraction significantly. CONCLUSION: This study proved that extraction using CTAB reverse micelles is a very effective method to separate hyperoside from Hypericum perforatum L. Under optimal conditions the extraction efficiency can reach 68.3% and the single‐strip‐extraction efficiency can reach 85.9%. The proportion of hyperoside among the flavonoids left in the strip‐extract can reach 93.3 wt%. This finding is very significant, because it demonstrates that reverse micellar extraction is a promising way to separate and purify materials with small molecules. Copyright © 2008 Society of Chemical Industry     

Synthesis of conductive microspheres by radiation polymerization

A conductive monodisperse microspheres consisting of poly(ethylene glycol)dimethacrylate and methyloxycarbonyl-bicyclo[2.2.1]hepta-2,5-diene was synthesized by radiation induced polymerization. Ionic conductivity and relative dielectric constant were found to be greatly dependent on the content of poly(ethylene glycol)methacrylate in the copolymer. The diameter of the microspheres was 0.48-0.86 μm, in which the irradiation was carried out without stabilizer at a dose rate of 20 kGy/h with ⁶⁰Co γ-ray.     

Facile fabrication of nanocomposite microspheres with polymer cores and magnetic shells by Pickering suspension polymerization

Pickering suspension polymerization was used to prepare magnetic polymer microspheres that have polymer cores enveloped by shells of magnetic nanoparticles. Styrene was emulsified in an aqueous dispersion of Fe₃O₄ nanoparticles using a high shear. The resultant Pickering oil-in-water (o/w) emulsion stabilized solely by magnetic nanoparticles was easily polymerized at 70 °C without stirring. Fe₃O₄ nanoparticles act as effective stabilizers during polymerization and as building blocks for creating the organic–inorganic hybrid nanocomposite after polymerization. The fabricated magnetic nanocomposites were characterized by FTIR, XRD, TGA, DSC, GPC, XPS and SEM. The structures of the polymer core and the nanoparticle shell were analyzed. We investigated the effects on the products of the weight of Fe₃O₄ nanoparticles used to stabilize the original Pickering emulsions. Pickering suspension polymerization provides a new route for the synthesis of a variety of hybrid nanocomposite microspheres with supracolloidal structures.     

Polyphenol oxidase in reverse micelles of AOT/cyclohexane: A thermostability study

Polyphenol oxidase catalysing the oxidation of 4‐methylcatechol in reverse micelles of AOT/cyclohexane had an optimum temperature 15 °C higher than in aqueous medium. However, the enzyme lost stability when it was preincubated in reverse micelles in the absence of substrate regardless of the temperature although the effect was more pronounced at higher temperatures. The thermostability of polyphenol oxidase is higher when it is injected in reverse micelles containing buffer than when injected in initially empty micelles. Moreover, the thermostability of polyphenol oxidase in reverse micelles is strongly dependent on the size of the micelles, the bigger the micelle the greater the stability. The thermoinactivation of the enzyme follows a monomolecular process characteristic of a conformational change so the protein is protected by ligands towards inactivation. p‐Nitrophenol as competitive inhibitor and acetyl tyrosine ethyl ester as alternate substrate increase the half‐life of the polyphenol oxidase by about 2.5 and 4 times respectively. This finding may allow the use of the enzyme at higher temperatures with a gain in its stability. © 2001 Society of Chemical Industry     

Increased activity and stability of Candida rugosa lipase in reverse micelles formed by chemically modified AOT in isooctane

Sodium bis (2‐ethylhexyl polyoxyethylene) sulfosuccinates, which can be structurally viewed as chemically modified AOT (MAOT), were prepared and successfully used to form reverse micelles in isooctane. The activity and stability of Candida rugosa lipase (glycerol‐ester hydrolase, EC 3.1.1.3) appreciably increased in the MAOT/isooctane reverse micellar system compared with the AOT/isooctane system taking the hydrolysis of olive oil as a model reaction. The best polymerization number of oxyethylene group was found to be 2.0, which corresponded to a maximum enzyme activity of twice that in the AOT/isooctane system. The half‐life of lipase in the MAOT micellar system was twice that in the AOT micellar system. The optimal operational conditions remained unchanged. The Michaelis kinetics showed that the maximum reaction rate obviously increased in the MAOT micellar system compared with that in the AOT micellar system, while the change in the Michaelis constant was insignificant. © 2001 Society of Chemical Industry     

Preparation of microspheres with silicone oil cores and poly(N‐isopropylacrylamide) shells by physical coating

Surfactant‐free thermoresponsive microspheres with a silicone oil cores surrounded by poly(N‐isopropylacrylamide) shells have been successfully prepared by physical coating method for the first time. The influences of reaction temperature, N‐isopropylacrylamide (NIPAM) dosage, and stirring rate on the formation, morphology, particle size, and monodispersity of microspheres were experimentally studied. In the preparation of microspheres, when reaction temperature was above the lower critical solution temperature of poly(N‐isopropylacrylamide), products had higher yield of particles and narrower size distribution. With increasing NIPAM dosage, the particle diameter became larger and the shell layer thickened and the monodispersity became better. With increasing stirring rate, the particle diameter and the monodispersity decreased obviously. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102:5571–5576, 2006     

两亲性聚乙二醇接枝聚乳酸胶束的制备及特性

制备聚乙二醇接枝聚乳酸(PPLA)聚合物胶束,探讨其作为药物载体的可行性和稳定性。溶剂挥发法制备PPLA胶束并对其表征。萘普生为模型药物,单因素考察了投药量、丙酮用量、加样顺序对包封率的影响。结果表明,PPLA临界胶束质量浓度(CMC)低,为3×10-4g/L;胶束呈球形、平均粒径小于200nm;在室温、稀释、碱性条件下稳定;最佳载药条件为:材料与药物同时溶于丙酮后滴入水中、丙酮与水的体积比1∶10,萘普生与PPLA质量比0.8∶10,PPLA胶束质量浓度1.0g/L。37℃时载药胶束在磷酸盐缓冲液(PBS)中可缓慢持续释放5d以上。结果证明,制备的聚乙二醇接枝改性聚乳酸聚合物胶束可用作疏水性药物的缓释给药载体。     

Hollow porous poly(lactic acid) microspheres

On the basis of the water solubility of poly(N‐vinyl‐2‐pyrrolidinone), hollow porous poly(lactic acid) microspheres (HPPLAs) were prepared by a water‐in‐oil‐in‐water multiple‐emulsion solvent evaporation method. The influence of the concentration of the stabilizer Span80 in the oil phase on the morphology was investigated. It was found that when the content of Span80 solutions was 3.5 wt %, most HPPLAs were about 2 μm in diameter. Field scanning electron microscopy results show that the HPPLAs were porous and hollow. The structure and crystal form of the HPPLAs were characterized by Fourier transform infrared spectroscopy and X‐ray diffraction analysis. Using these HPPLAs as degradable templates, we successfully synthesized Litchi‐like polystyrene (PS) microspheres about 2 μm in diameter by the emulsion method. When used as drug carriers, these HPPLAs would be convenient in which to embed drugs, whereas the Litchi‐like PS microspheres may have potential as new materials for polymer modification. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Preparation of hollow poly(imino ether ketone) microspheres by microliquid technique

1, 4‐bis (4‐amiophenoxy) benzene and 1, 4‐Bis (4‐bromobenzoyl) benzene as monomers, poly(imino ether ketone) (PIEK) was synthesized via palladium‐catalyzed aryl amination reaction. Based on the good chemical and physical properties, big diameter (0.6–2 mm) hollow microspheres of PIEK, used for Inertial Confinement Fusion research, were prepared by using the microliquid technique and double‐layer latex technique. A new double T‐channel droplet generator was designed and developed for fabrication of controlled‐size PIEK hollow microspheres continuously. Study on manipulative condition of diameter and thickness of microspheres was done, and density matching impacting on the quality of shells was discussed. The structures of the PIEK hollow microspheres were characterized, and they possessed equal wall thickness and good spherical symmetry. The properties of the microspheres were detected, and the results showed that they showed good stability under cold environment and high temperature. Additionally, the PIEK hollow microspheres exhibited good mechanical and anti‐irradiation properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Synthesis of pH-sensitive hollow polymer microspheres with movable magnetic core

The pH-sensitive hollow poly(N,N′-methylenebisacrylamide-co-methacrylic acid) (P(MBAAm-co-MAA)) microspheres with movable magnetic/silica (Fe₃O₄/SiO₂) cores were prepared by the selective removal of poly(methacrylic acid) (PMAA) layer in ethanol/water from the corresponding Fe₃O₄/SiO₂/PMAA/P(MBAAm-co-MAA) tetra-layer microspheres, which were synthesized by the distillation precipitation copolymerization of N,N′-methylenebisacrylamide (MBAAm) and methacrylic acid (MAA) in the presence of Fe₃O₄/SiO₂/PMAA tri-layer microspheres as seeds in acetonitrile with 2,2′-azobisisobutyronitrile (AIBN) as the initiator. The Fe₃O₄/SiO₂/PMAA tri-layer microspheres were afforded by the distillation precipitation polymerization of MAA with 3-(methacryloxy)propyl trimethoxysilane (MPS)-modified Fe₃O₄/SiO₂ core-shell particles as the seeds. The functional multi-layer inorganic/polymer microspheres and the corresponding hollow polymer microspheres with movable magnetic cores were characterized with transmission electron microscopy (TEM), Fourier-transform infrared (FT-IR) spectra, dynamic light scattering (DLS), and vibrating sample magnetometer (VSM).