Synthesis of novel magnetic polymer microspheres with amphiphilic structure

Novel magnetic polymer microspheres with amphiphilic structure ranging in diameter from 5 to 80 μm were prepared by dispersion copolymerization of styrene and poly(ethylene oxide) acrylamide macromonomer (MPEO) in the presence of Fe₃O₄ magnetic fluid. The effects of various polymerization parameters on the average particle size were systematically investigated. The average particle size was found to increase with increasing initiator concentration. It also increased with decreasing stabilizer concentration and MPEO concentration. The content of the amino groups localized in the microspheres ranged from 0.01 to 0.25 mmol/g. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1879–1884, 2003     

Preparation and characterization of magnetic amphiphilic polymer microspheres

Magnetic amphiphilic polymer microspheres were prepared by copolymerization of styrene with poly(ethylene oxide) macromonomer (MPEO) in the presence of Fe₃O₄ magnetic fluid in ethanol/water medium. Magnetic microsphere size, size distribution, and surface morphology were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM). The structure of copolymer was determined by infrared spectroscopy. With increasing MPEO used in the polymerization, the resulting microsphere size decreased. Magnetic amphiphilic polymer microspheres containing 0.02–0.2 mmol/g hydroxyl groups could be prepared by using different MPEO concentration. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1847–1851, 2001     

A new synthetic approach to asymmetric amphiphilic ABA′ block copolymers by ATRP and click reactions

Well‐defined asymmetric amphiphilic ABA′ block copolymers composed of poly(ethylene oxide) monomethylene ether (MPEO) with different molecular weights as A or A′ block and poly(styrene) (PS) as B block were synthesized by the combination of atom transfer radical polymerization (ATRP) and click reactions. First, bromine‐terminated diblock copolymer poly(ethylene oxide) monomethylene ether‐block‐poly(styrene) (MPEO‐PS‐Br) was prepared by ATRP of styrene initiated with macroinitiator MPEO‐Br, which was prepared from the esterification of MPEO and 2‐bromoisobutyryl bromide. Then, the azido‐terminated diblock copolymers MPEO‐PS‐N₃ were prepared through the bromine substitution reaction with sodium azide. Propargyl‐terminated MPEO with a different molecular weight was prepared under the basic condition from propargyl alcohol and p‐toluenesulfonyl‐terminated MPEO, which was prepared through the esterification of MPEO and p‐toluenesulfochloride using pyridine as solvent. Asymmetric amphiphilic ABA′ block copolymers, with a wide range of number–average molecular weights from 1.92 × 10⁴ to 2.47 × 10⁴ and a narrow polydispersity from 1.03 to 1.05, were synthesized via a click reaction of the azido‐terminated diblock copolymers and the propargyl‐terminated MPEO in the presence of CuBr and 1,1,4,7,7‐pentamethyldiethylenetriamine (PMDETA) catalyst system. The structures of these ABA′ block copolymers and corresponding precursors were characterized by NMR, IR, and GPC. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and characterization of magnetic poly(styrene–glycidyl methacrylate) microspheres for highly efficient protein adsorption by two‐stage dispersion polymerization

Micrometer‐sized superparamagnetic poly(styrene–glycidyl methacrylate)/Fe₃O₄ spheres were synthesized by two‐stage dispersion polymerization with modified hydrophobic Fe₃O₄ nanoparticles, styrene (St), and glycidyl methacrylate (GMA). The morphology and properties of the magnetic Fe₃O₄–P (St‐GMA) microspheres were examined by scanning electron microscopy, transmission electron microscopy, vibrating sample magnetometry, thermogravimetric analysis, and attenuated total reflectance. The average size of the obtained magnetic microspheres was 1.50 μm in diameter with a narrow size distribution, and the saturation magnetization of the magnetic microspheres was 8.23 emu/g. The magnetic Fe₃O₄–P (St‐GMA) microspheres with immobilized iminodiacetic acid–Cu²⁺ groups were used to investigate the adsorption capacity and selectivity of the model proteins, bovine hemoglobin (BHb) and bovine serum albumin (BSA). We found that the adsorption capacity of BHb was as high as 190.66 mg/g of microspheres, which was 3.20 times greater than that of BSA, which was only 59.64 mg/g of microspheres as determined by high‐performance liquid chromatography. With a rather low nonspecific adsorption, these microspheres have great potential for protein separation and purification applications. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43005.     

Controlled preparation of Fe3O4/P (St-MA) magnetic composite microspheres by DPE method

In this work, controlled radical polymerization based on 1, 1-diphenylethylene (DPE method) was used to prepare magnetic composite microspheres. By this method, Fe₃O₄/P (St-MA) magnetic composite microspheres were prepared via copolymerization of styrene (St) and maleic anhydride (MA) using DPE as radical control agent in the presence of Fe₃O₄ nanoparticles. The structure and properties of the magnetic composite microspheres obtained were characterized by IR, ¹H-NMR, SEC-MALLS, TEM, TGA, VSM, DLS and other instruments. It was found that the DPE method allows the controlled preparation of magnetic composite microspheres, and Fe₃O₄/ P(St-MA) microspheres possess perfect sphere-shaped morphology, homogeneous particle size, carboxylic surface, superparamagnetism with a saturation magnetization of 14.704 emu/g, and magnetic content with a value of 25%.     

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     

Synthesis and characterization of air‐stable magnetic Fe composites microspheres of narrow size distribution

Air‐stable Fe magnetic nanoparticles entrapped within carbon and porous crosslinked polystyrene microspheres of narrow size distribution were prepared by the following sequential steps: (1) Polystyrene/poly(divinyl benzene) and polystyrene/poly(styrene‐divinyl benzene) uniform micrometer‐sized composite particles were prepared by a single‐step swelling of uniform polystyrene template microspheres dispersed in an aqueous continuous phase with emulsion droplets of dibutyl phthalate containing the monomers divinyl benzene and styrene and the initiator benzoyl peroxide. The monomers within the swollen polystyrene template microspheres were then polymerized by raising the temperature to 73°C; (2) Porous poly (divinyl benzene) and poly(styrene‐divinyl benzene) uniform crosslinked microspheres were prepared by dissolution of the polystyrene template part of the former composite particles; (3) Uniform magnetic poly(divinyl benzene)/Fe and poly(styrene‐divinyl benzene)/Fe composite microspheres were prepared by entrapping Fe(CO)₅ within the porous crosslinked microspheres, by suction of the Fe complex into the dried porous particles, followed by decomposition of the encapsulated Fe(CO)₅ at 200°C in Ar atmosphere; (4) Uniform magnetic air‐stable C/Fe composite microspheres were prepared similarly, apart from changing the decomposition temperature from 200 to 600°C. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Factors influencing magnetic polymer microspheres prepared by dispersion polymerization

Magnetic iron oxide (Fe₃O₄) was prepared by a coprecipitation method. Core–shell composite magnetic polymer microspheres with carboxyl groups were synthesized by the dispersion polymerization of styrene and acrylic acid in the presence of magnetic oxide, and dibenzoyl peroxide was used as an initiator. The synthesized magnetic polymer microspheres were characterized with X‐ray diffraction, transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, and so forth. The results indicated that the product was single‐phase Fe₃O₄, and its average size was about 10 nm. The configuration of the microspheres, which contained carboxyl groups, was spherical, and the average size was about 2 μm. The results of vibrating sample magnetometry tests showed that the magnetic powders produced by different surfactants had different saturation magnetizations. When poly(ethylene glycol) with a weight‐average molecular weight of 4000 was used as a surfactant, the saturation magnetization of the samples reached 69.2 emu/g. The factors that affected the shape, magnetism, size, and distribution of the microspheres were also studied. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Preparation and characterization of magnetic composite microspheres using a free radical polymerization system consisting of DPE

In this paper, a free radical polymerization system consisting of DPE was used to prepare magnetic composite microspheres. Fe₃O₄/P(AA-MMA-St) core-shell magnetic composite microspheres have been synthesized by copolymerization of acrylic acid, methyl methacrylate and styrene using DPE as radical control agent in the presence of Fe₃O₄ nanoparticles. The structure and properties of the magnetic composite microspheres were analyzed by FTIR, ¹H NMR, SEC-MALLS, TEM, TGA, VSM and other instruments, and the formation mechanism of composite microspheres was supposed by those results. It was found that the Fe₃O₄/P(AA-MMA-St) microspheres were nano-size with relatively homogeneous particle size distribution, perfect sphere-shaped morphologies, superparamagnetism with a saturation magnetization of 18.430 emu/g, and high magnetic content with a value of 40%. ¹H NMR and TEM analysis indicated that at the first stage of polymerization, a DPE-containing copolymer of acrylic acid, methyl methacrylate formed and was then absorbed on the surface of Fe₃O₄ nanoparticles. Contact angle analysis indicated that the DPE-containing copolymer improved hydrophobicity of Fe₃O₄ nanoparticles through chemical absorption. In the second step polymerization, certain amount of monomers of styrene and residue methacrylate were initiated by the DPE-containing copolymer on the Fe₃O₄ nanoparticles' surface and resulted in the formation of Fe₃O₄/P(AA-MMA-St) composite microspheres.     

Kinetics of polymerization and particle stabilization mechanism on dispersion copolymerization of styrene and divinylbenzene

Monodisperse highly crosslinked microspheres were prepared by dispersion copolymerization of styrene and divinylbenzene in an ethanol/water medium using poly(N‐vinylpyrrolidone) (PVP) as the stabilizer. The locus of polymerization and growth of particles were investigated. The polymerization kinetics, average particle diameter (D_n), polydispersity index (PDI), and numbers of particles (N_p) were presented. When the initial styrene concentration is below 20%, the results indicate that the polymerization occurs in the particles, and the particles grow to their final size by the diffusion of monomer and oligomer into the existing particles. The polymerization rate can be described by the equation R_p = k[l]^0.87 ([St]^1.91 + [DVB]^0.09) (1 + [PVP]^0.01) exp(? 45.35/RT). The data from infrared spectroscopy demonstrated that the graft stabilizer was present. The dissolution experiments show that the crosslinking reaction occurred irregularly in batch dispersion polymerization. Using the postaddition approach, up to 3% divenylbenzene (DVB) was successfully incorporated in the synthesis of coagulum‐free substance, and monodisperse crosslinked 5 μ m microspheres with a superior resistance to solvents have been prepared. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2230–2238, 2002     

Synthesis of monodisperse styrene/methyl methacrylate/acrylic acid latex using surfactant‐free emulsion copolymerization in air

Monodisperse styrene/methyl methacrylate/acrylic acid (St/MMA/AA) copolymer microspheres have been prepared with surfactant‐free emulsion polymerization in air. The presence of oxygen in the system not only caused an induction period but also decreased the average particle size (D_p). However increasing AA concentration ([AA]) gave a reduction in the induction period. The FTIR and NMR analysis of the latex copolymer confirmed that the correlation of the copolymer compositions with the feed compositions was much better at the lower [AA] than at the higher levels. The AA contents of the copolymers obtained in air were much lower than those of the copolymers obtained under N₂ protection. Decreasing [AA] led to decrease in the copolymer molecular weight and broadening of the molecular weight distribution, but the particle size distribution (δ/D_p) was unaffected. In addition, the average particle diameter (D_p) was proportional to [AA]^–0.255, and increasing comonomers feed content caused linear increase of D_p, and a monodisperse sample with final solids contents up to 34.2 wt % was obtained. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

PEG-modified magnetic hypercrosslinked poly(styrene-co-divinylbenzene) microspheres to minimize sorption of serum proteins

Monodisperse poly(styrene-co-divinylbenzene) [P(St-DVB)] microspheres were prepared by the precipitation polymerization of styrene (St) and divinylbenzene (DVB) in acetonitrile (ACN). Effect of St/DVB ratio and monomer concentration on morphology and particle size was investigated. Monodisperse 4.1 μm P(St-DVB) microspheres were chloromethylated with chloromethyl methyl ether (CMME) and hypercrosslinked using anhydrous FeCl₃ as a catalyst to form a very fine porous structure and to introduce reactive chloromethyl groups in the resulting product denoted as HC-P(St-DVB) particles. The hypercrosslinked microspheres were then functionalized with amino groups to yield HC-P(St-DVB)-NH₂ particles and iron oxide was precipitated within their pores. The obtained microparticles were highly magnetic with iron content ～38 wt% Fe. The surface of the magnetic microspheres was newly hydrophilized with methoxy-poly(ethylene glycol) (methoxy-PEG) which was confirmed by ATR FT-IR spectroscopy. The poly(ethylene glycol) (PEG)-modified magnetic microspheres were investigated in terms of sorption of serum proteins under different conditions and compared with the sorption on neat magnetic HC-P(St-DVB)-NH₂ particles. The surface modification of magnetic microspheres significantly minimized the adsorption of the serum proteins.     

Preparation and assembly performance of colloidal particles of photonic crystals with controlled photonic band gaps

Monodisperse microspheres with average particle size in the range of 100–600 nm, whose main monomer was styrene, were prepared by soap-free emulsion polymerization. The factors influencing polymer colloidal particle sizes and size distributions were investigated, including initiator concentration, polymerization temperature and hydrophilic monomer amount. Then, six kinds of polymer microspheres with average size from 153 nm to 565 nm were selected to grow colloid photonic crystal by vertical deposition method. Results showed that photonic band gaps could be effectively adjusted by changing the particle size. The obtained photonic crystals were highly ordered face-centered cubic structures. Furthermore, vertical deposition was only suitable for particles with average size less than 300 nm.     

Preparation of magnetic poly(lactic‐co‐glycolic acid) microspheres with a controllable particle size based on a composite emulsion and their release properties for curcumin loading

Because of their unique magnetic features and good biocompatibility, magnetic poly(lactic‐co‐glycolic) acid (PLGA) microspheres have great application potential in magnetic targeted drug‐delivery systems. In this research, magnetic PLGA microspheres with controllable particle sizes were successfully prepared from a composite emulsion with a T‐shaped microchannel reactor. A water‐in‐oil‐in‐water composite emulsion was generated by the injection of a dichloromethane/gelatin water‐in‐oil initial emulsion into the microchannel together with a coating aqueous phase, that is, the aqueous solution of glucose and poly(vinyl alcohol). The mean particle size of the microspheres could be controlled by the manipulation of the osmotic pressure difference between the internal and external aqueous phases via changes in the glucose concentration. Curcumin, a drug with an inhibitory effect on tumor cells, was used to exemplify the release properties of the magnetic PLGA microspheres. We found that the mean particle size of the microspheres ranged from 16 to 207 μm with glucose concentrations from 0 to 20 wt %. The resulting microspheres showed a rapid magnetic response, good superparamagnetism, and a considerable magnetocaloric effect, with a maximum magnetic entropy of 0.061 J·kg^?1·K^?1 at 325 K. An encapsulation efficiency of up to 77.9% was achieved at a loading ratio of 3.2% curcumin. A release ratio of 72.4% curcumin from the magnetic PLGA microspheres was achieved within 120 h in a phosphate‐buffered solution. The magnetic PLGA microspheres showed potential to be used as drug carriers for magnetic targeted tumor therapy. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43317.     

Synthesis of Core/Shell Magnetic Porous Microspheres for Lipase Immobilization

Magnetic porous hydrophobic microspheres were prepared by modified suspension copolymerization of methacrylate (MMA) and divinylbenzene (DVB) in the presence of oleic acid coated magnetite (Fe₃O₄), and the microspheres were used as biocarrier for the lipase immobilization. The results showed that the magnetic microspheres possessed spherical shape, core/shell structure, porous structure and high magnetic content, and the size and structure of magnetic microspheres had no significant changes after enzyme binding. The particle average size of microspheres was 66 μm, the magnetic content of microspheres was up to 31%, and the magnetization saturation values of the core/shell magnetic microspheres were measured at 300 K to be 11.02 emu g⁻¹. Lipase was immobilized on the magnetic porous carrier at up to 16.30 mg/g carrier. Activity and enantioselectivity of the immobilized lipase for the synthesis of R-HMPC acetate were investigated, indicating an interfacial activation of the enzyme after immobilization. Moreover, the pH dependency and operational stability of the immobilized lipase were studied, and they possess high stability and can be reused for ten cycles with loss 10% activity.     

Emulsion–ion extraction technique for synthesis of hollow bicomponent oxide microspheres

Abstract

H ollow ox ide microspheres in the bicomponent systems Al₂O₃-28 wt-%SiO₂ (AS) ( mullite) , Al₂O₃- 13 wt-%T iO₂ (AT) , and Z rO₂-10 wt-%Y₂O₃ ( Z Y) were prepared by the emulsion-ion extraction technique. Monodisperse microsphere formation was found to depend on the experimental parameters adopted during ion ex traction and the surfactant concentration present in the emulsion system. Powder characteristics were investigated using X-ray diffraction, optical and scanning electron microscopy, and particle size analysis. The gel microspheres in the AS, AT , and ZY systems started crystallising at about 900, 800, and 400 °C respectively. The oxide microspheres were mostly spherical in morphology and the sphericity was retained even after calcination at 1300 °C for 1 h. Formation of hollow microspheres with a single spherical cavity was identified by SEM . All oxide microspheres calcined at 1300 °C for 1 h ex hibited a particle size distribution within the range 5-60 μm, the average size ( d₅₀) varying from 19 to 22 μm. BCT / 537     

Control of monodisperse particle size of styrenic–acrylate copolymers in dispersion copolymerization

Syntheses of monodisperse poly[(styrene)‐co‐(n‐butyl acrylate)] and poly[(styrene)‐co‐(2‐ethylhexyl acrylate)] were carried out by dispersion polymerization. The reactions were performed in the mixed solvent of ethanol–water in the presence of azo‐bisisobutyronitrile and poly(N‐vinylpyrrolidone) as the initiator and dispersant, respectively. The effects of reaction parameters, that is the type and concentration of dispersant, ratio of the mixed solvent, reaction temperature, agitation rate, monomer composition between styrene and n‐butyl acrylate or 2‐ethylhexyl acrylate, crosslinking agent and reaction time on the particle size, size distribution and average molecular weights of the resulting copolymer were thoroughly investigated. The resulting copolymer particles were smooth on their spherical surface and the sizes were in the range 0.6–1.8 µm with a narrow size distribution. In most cases, a correlation between small particle sizes with high average molecular weights was observed. The average particle size generally increased with increasing reaction temperature, time and acrylate monomer content. In contrast, the particle size decreased as the molecular weight, concentration of dispersant, polarity of the medium or agitation rate was increased. The glass transition temperature (T_g) of the copolymers can be controlled by the mole ratio of the comonomer. The T_g values decreased when the content of acrylate monomers in the copolymer increased, and T_g values of the synthesized copolymer were in the range 66–102 °C. Instead of using n‐butyl acrylate monomer in the copolymerization, 2‐ethylhexyl acrylate copolymerization with styrene resulted in insignificant changes in the particle sizes but there were significant decreases in T_g values. In this study, the monodisperse particles can be obtained by monitoring the appropriate conditions regarding PVP K‐30 (2–8 wt%), ethanol/water (90/10 wt%), the reaction temperature (70 °C) and the agitation rate (100 rpm). © 2000 Society of Chemical Industry     

Uniform star‐polystyrene nanoparticles prepared by emulsion atom transfer radical polymerization

Pentaerythritol (PT) was converted into four‐arm initiator pentaerythritol tetrakis(2‐chloropropionyl) (PT‐Cl) via reaction with 2‐chloropropionyl chloride. Uniform (monodisperse) star‐polystyrene nanoparticles were prepared by emulsion atom transfer radical polymerization of styrene, using PT‐Cl/CuCl/bpy (bpy is 2,2′‐dipyridyl) as the initiating system. The structures of PT‐Cl and polymer were characterized by Fourier transform infrared spectroscopy and nuclear magnetic resonance. The morphology, size and size distribution of the star‐polystyrene nanoparticles were characterized by transmission electron microscopy, atomic force microscopy and photon correlation spectroscopy. It was found that the average diameters of star‐polystyrene nanoparticles were smaller than 100 nm (30–90 nm) and monodisperse; moreover, the particle size could be controlled by the monomer/initiator ratio and the surfactant concentration. The average hydrodynamic diameter (D_h) of the nanoparticles increased gradually on increasing the ratio of styrene to PT‐Cl and decreased on enhancing the surfactant concentration or increasing the catalyst concentration. Copyright © 2011 Society of Chemical Industry     

Dependence of morphological changes of polymer particles on hydrophobic/hydrophilic additives

Fairly uniform microspheres of poly(styrene‐co‐methyl methacrylate) were prepared by employing a microporous glass membrane [Shirasu porous glass (SPG)]. The single‐step SPG emulsification, the emulsion composed mainly of monomers, hydrophobic additives, and an oil‐soluble initiator, suspended in the aqueous phase containing a stabilizer and inhibitor, was then transferred to a reactor, and subsequent suspension polymerization followed. The droplets obtained were polymerized at 75°C under a nitrogen atmosphere for 24 h. The uniform poly(styrene‐co‐methyl methacrylate) microspheres with diameters ranging from 7 to 14 μm and a narrow particle‐size distribution with a coefficient of variation close to 10% were prepared by using SPG membrane with a pore size of 1.42 μm. The effects of the crosslinking agent and hydrophobic additives on the particle size, particle‐size distribution, and morphologies were investigated. It was found that the particle size decreased with a narrower size distribution when the additives were changed from long‐chain alkanes to long‐chain alcohols and long‐chain esters, respectively. Various microspheres with different morphologies were obtained, depending on the composition of the oil phase. The spherical poly(styrene‐co‐methyl methacrylate) particles without phase separation were obtained when using an adequate amount of the crosslinking agent and methyl palmitate as an additive. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 1013–1028, 2000     

Preparation of Raspberry-Like Adsorbed Silica Nanoparticles via Miniemulsion Polymerization Using a Glycerol-Functionalized Silica Sol

A series of polymer/SiO₂ organic-inorganic composite microspheres were successfully prepared through miniemulsion polymerization. A TEM study indicated that the composite microspheres had raspberry-like morphology and silica particles were successfully deposited onto the surfaces of organic polymer microspheres. The average particle size and the silica content of composite microspheres could range from 180 nm to 240 nm and 15 ～ 35 wt%, respectively. The influence of reaction conditions such as the amount of emulsifier, the sonification frequency and sonification time, the amount of silica sol, butyl acrylate (BA) on the particle size, silica content and morphology of composite microspheres have been studied.