Titanium dioxide/poly(methyl methacrylate) composite microspheres prepared by in situ suspension polymerization and their ability to protect against UV rays

Homogenously dispersed TiO₂/poly(methyl methacrylate) (PMMA) composite microspheres were produced in the size range of 1-10µm and the interfacial characteristics of TiO₂ and PMMA in suspension polymerization were considered. In electron microscopy observation, it was found that TiO₂ nanoparticles were embedded homogeneously in the PMMA phase. This study elucidates that the interfacial compatibility between TiO₂ and PMMA played a decisive role in producing the composite microspheres structured with inner TiO₂ and continuous PMMA, which was achieved by treating the surface of the TiO₂ particles hydrophobically. The TiO₂/PMMA composite microspheres produced showed good ability to protect against UV rays and are therefore of great usefulness in cosmetic formulations.     

Mechanism of the formation of stable microspheres by precipitation copolymerization of styrene and divinylbenzene

Fully crosslinked, stable poly(styrene‐co‐divinylbenzene) microspheres were prepared by precipitation polymerization, and a new mechanism is proposed, based on the morphology, circularity, and specific surface area. Once the stable particles were generated by aggregation of the primary nucleus particles, they grew in size by absorbing oligomeric species without generating substantial pores. The investigation was carried out characterizing the particles in the polymerization time and in various concentrations of the polymerization ingredients. Particle size continuously grew, but the uniformity and circularity of the microspheres were reduced with polymerization time because of the higher reactivity of divinylbenzene. The measured specific surface areas of the microspheres all were less than 10 m²/g, which showed good agreement with calculated values under an assumption of no pores on the surface of the microspheres. Thus, the specific surface area of the microspheres supported the proposed mechanism. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 3967–3974, 2004     

Preparation and Metal Sorption Properties of GMA-MMA-DVB Microspheres Functionalized with 2-Aminothiazole

Crosslinked glycidylmethacrylate-methylmethacrylate-divinylbenzen (GMA-MMA-DVB) microspheres were prepared by suspension polymerization. The GMA-MMA-DVB microspheres with an average size of 150–300 μm and surface area of 1.51 m²g^?1 were functionalized with 2-aminothiazole (ATAL). The affinity of the functionalized microspheres for copper, iron, aluminum, lead, cobalt, and nickel ions was examined. The effects of pH, resin amount, shaking time, type, and volume of the elution solution on the sorption and desorption properties of functionalized microspheres for these metal ions were investigated using the batch method. Sorption capacities (0.97–1.12 mmolg^?1), quantitation limits (2.6–3.0 ppb) and recoveries (90–99%) were calculated.     

Synthesis and characterization of azoxystrobin hydrophilic molecularly imprinted microspheres

Abstract

In this research, hydrophilic molecularly imprinted microspheres (HMIPs) for azoxystrobin were successfully synthesized through precipitation polymerization. The adsorption capacities of HMIPs for azoxystrobin in water medium were higher than ordinary molecularly imprinted microspheres (MIPs), and HMIPs exhibited good hydrophilic properties. HMIPs and non-imprinted microspheres (HNIPs) were characterized by FT-IR, SEM, laser particle size analyzer and TGA. Comparing with HNIPs, azoxystrobin had a significant influence on morphologys and sizes of HMIPs. The Langmuir adsorption isotherm illustrated each binding site of HMIPs had the same adsorption capacity. The Lagergran pseudo-second-order kinetic model indicated the adsorption process between azoxystrobin and HMIPs was chemical adsorption. BET test illustrated HMIPs had bigger specific surface areas than HNIPs. Selective adsorption indicated that HMIPs had highly specific recognition of azoxystrobin. HMIPs successfully exhibited high selectivity and high hydrophilicity in water medium.     

Poly(N,N‐dimethylacrylamide)‐Based Microspheres Prepared by Heterogeneous Polymerizations

PDMAAm microspheres have been obtained by inverse suspension, inverse emulsion, and dispersion polymerization. Conventional inverse suspension polymerization in toluene/trichloroethene is modified by the use of ultrasound. The resulting hydrogel microspheres are examined by dynamic light scattering and scanning electron microscopy to afford the morphology, dispersity, and size of the microspheres. Inverse suspension polymerization yields 100‐µm particles, while those obtained by inverse emulsion polymerization are 0.13–1 µm in diameter. While the inverse techniques produce particles of broad size distribution, monodisperse microspheres are obtained by the Kraton G 1650‐stabilized dispersion polymerization of DMAAm in a toluene/heptane medium. The particle size and polydispersity could be controlled by the addition of water into the dispersed phase, and by varying the cellulose acetate butyrate or Kraton G 1650 concentration and the toluene/trichloroethene or toluene/heptane ratio.

     

Synthesis and Characterization of β‐CD‐Coated Polystyrene Microspheres by γ‐Ray Radiation Emulsion Polymerization

Polystyrene (PS) microspheres coated with β‐cyclodextrin (β‐CD) were fabricated via γ‐ray‐induced emulsion polymerization in a ternary system of styrene/β‐CD/water (St/β‐CD/water). The solid inclusion complex of St and β‐CD particles formed at the St droplets–water interface can stabilize the emulsion as the surfactant. TEM and XPS results showed that β‐CD remains on the surface of PS particles. The average size of the PS particles increases from 186 to 294 nm as the weight ratio of β‐CD to St rises from 5% to 12.5%. The water contact angle (CA) of PS latex film is lower than 90°, and reduces with the β‐CD content even to 36°. Thus, this work provides a new and one‐pot strategy to surface hydrophilic modification on hydrophobic polymer particles with cyclodextrins through radiation emulsion polymerization.     

Multihollow structured poly(methyl methacrylate)/silver nanocomposite microspheres prepared by suspension polymerization in the presence of dual dispersion agents

Poly(methyl methacrylate) (PMMA)/silver nanocomposite microspheres with unique multihollow structures were prepared by suspension polymerization in the presence of dual dispersion agents. The addition of a lipophilic emulsifier, polyethylene glycol (30EO) dipolyhydroxystearate (Arlacel P135), not only stabilized water-in-oil (W/O) emulsion, but also converted silver nanoparticles from hydrophilic to lipophilic. When a suspension polymerization dispersion agent, poly(vinyl alcohol), was added to the above W/O emulsion system, a water-in-oil-in-water suspension was formed with silver nanoparticles dispersed in the oil phase. The suspension polymerization was carried out at low temperature with 2,2’-azobis(2,4-dimethylvaleronitrile) as the initiator. When modified silver nanoparticles were added, the rate of polymerization increased slightly. High monomer conversion (about 85%) was obtained in spite of low polymerization temperature of 30 °C. Under controlled conditions, PMMA/silver microspheres with various hollow structures were synthesized. The PMMA/silver microspheres with multihollow structure showed high antibacterial ability.     

A new type of monodisperse porous, hydrophilic microspheres with reactive chloroalkyl functionality: synthesis and derivatization properties

A seeded polymerization method based on a new functional monomer, 3-chloro-2-hydroxypropyl methacrylate (HPMA-Cl), was proposed for the synthesis of a new type of monodisperse porous, hydrophilic microspheres with reactive character. By applying the method, poly(3-chloro-2-hydroxypropyl methacrylate-co-ethylene dimethacrylate) (poly(HPMA-Cl-co-EDMA)) microspheres in the range of 4–7 μm, with specific surface areas between 2 and 146 m²/g, were obtained. The microspheres are hydrophilic in nature due to the hydroxyl groups and are easily derivatizable due to the reactive chloropropyl moiety. Ligands in the form of small molecules carrying hydrophobic alkyl or hydrophilic ion exchanger groups were covalently attached onto the microspheres via simple and one-pot reactions via their chloropropyl functionality. Using the same functionality, click chemistry and surface-initiated atom transfer radical polymerization were also applied for the generation of triazole ring and zwitterionic molecular brushes on the microspheres, respectively. Poly(HPMA-Cl-co-EDMA) microspheres seem to be a promising hydrophilic reactive material particularly for the synthesis of ion exchanger resins and chromatographic stationary phases.     

Synthesis of functional magnetic porous SrFe<Subscript>12</Subscript>O<Subscript>19</Subscript>/P(St-DVB-MAA) microspheres by a novel suspension polymerization

In this study, a novel and effective suspension polymerization has been employed to prepare functional magnetic porous SrFe₁₂O₁₉/P(St-DVB-MAA) microspheres in the presence of bilayer surfactants (sodium dodecyl benzene sulfonate (SDBS) and oleic acid (OA)) coated on micro-size magnetic SrFe₁₂O₁₉. This was achieved by pre-polymerizing the organic phase, which contained co-monomers, porogens and treated magnetic particles, at 65°C for 0.5 h under ultrasound conditions. Aqueous solutions containing a dispersion agent were then added to effect suspension polymerization. Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD), thermogravimetric analysis (TGA) and magnetic property measurement system (MPMS) were used to characterize the functional magnetic porous microspheres. The results show that the microparticles are well shaped with a uniform size distribution of about 0.5 ∼ 0.7 mm and the surfaces of the microspheres have many micro-pores with an average diameter of 0.533 μm. There are carboxyl groups (−COOH) on the surface of the microspheres to the extent of 0.65 mmol g⁻¹, as determined by conductometric titration. According to the XRD spectra, iron oxide consists mainly of SrFe₁₂O₁₉ which reveals hexahedral structure. The content of magnetic SrFe₁₂O₁₉ reaches 17.81% (by mass), and the microspheres have good heat resistance. The magnetic porous microspheres are ferromagnetic with high residual magnetization and coercivity, 21.59 emu g⁻¹ and 4.13 kOe, respectively. The saturation magnetisation is around 42.85 emu g⁻¹.      

Preparation and surface modification of magnetic poly(methyl methacrylate) microspheres

~~Preparation and surface modification of magnetic poly(methyl methacrylate) microspheres~~     

One‐stage synthesis of narrowly dispersed polymeric core‐shell microspheres

A method of one‐stage soap‐free emulsion polymerization to synthesize narrowly dispersed core‐shell microspheres is proposed. Following this method, core‐shell microspheres of poly(styrene‐co‐4‐vinylpyridine), poly(styrene‐co‐methyl acrylic acid), and poly[styrene‐co‐2‐(acetoacetoxy)ethyl methacrylate‐co‐methyl acrylic acid] are synthesized by one‐stage soap‐free emulsion polymerization of a mixture of one or two hydrophobic monomers and a suitable hydrophilic monomer in water. The effect of the molar ratio of the hydrophobic monomer to the hydrophilic one on the size, the core thickness, and the shell thickness of the core‐shell microspheres is discussed. The molar ratio of the hydrophobic and hydrophilic monomers and the hydrophilicity of the resultant oligomers of the hydrophilic monomer are optimized to synthesize narrowly dispersed core‐shell microspheres. A possible mechanism of one‐stage soap‐free emulsion polymerization to synthesize core‐shell microspheres is suggested and coagglutination of the oligomers of the hydrophilic monomers on the hydrophobic core is considered to be the key to form core‐shell microspheres. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1192–1202, 2008     

Superabsorbent poly(acrylamide-co-itaconic acid) hydrogel microspheres: Preparation,characterization and absorbency

Poly(acrylamide-co-itaconic acid) (P(AM-co-IA)) hydrogel microspheres were prepared via inverse suspension polymerization method. DLS results showed the formation of the monodispersed hydrogel microspheres. The size of the hydrogel microspheres could be controlled by polymerization parameters. Absorbencies of P(AM-co-IA) microspheres in water and saline were investigated and calculated by size changes of each particle before and after swelling. The results showed that P(AM-co-IA) had high absorbencies, the weight of swollen particles was above 4000 times to that of the original dried microspheres. The superabsorbent hydrogel microspheres might find the potential applications in the fields of soil amendments, water shutoff agents, and drug delivery carriers.     

Precipitation polymerization in acetonitrile and 1‐propanol mixture: synthesis of monodisperse poly(styrene‐co‐divinylbenzene) microspheres with clean and smooth surface

Precipitation polymerization of styrene (St)–divinylbenzene (DVB) has been carried out using acetonitrile/1‐propanol mixture as the reaction media and 2,2′‐azobisisobutyronitrile (AIBN) as initiator. Monodisperse micron‐sized poly(St‐co‐DVB) microspheres with clean and smooth surface were synthesized in the absence of any stabilizing agent such as surfactants or steric stabilizers. The effects of various polymerization parameters such as 1‐propanol fraction in the reaction media, initiator and total monomer concentration, DVB content, polymerization time and polymerization temperature on the morphology, particle size and size distribution were investigated. It was found that smoothly shaped stable particles were obtained when less than 70 vol% of 1‐propanol was used in the media. The particle size increased with the AIBN concentration, whereas the change of uniformity was less obvious. Monodisperse microspheres were obtained when the total monomers loading ranged from 0.5 to 3 vol%. The particle diameter ranged from 2.73 to 1.87 µm with an increasing DVB content and the uniformity was enhanced. In addition, the yield of microspheres increased with the increasing total monomer, initiator, and DVB concentration and polymerization time. Copyright © 2010 John Wiley & Sons, Ltd.     

Porous monodisperse poly(divinylbenzene) microspheres by precipitation polymerization

The precipitation polymerization of commercial divinylbenzene in acetonitrile containing up to 40 vol. % toluene or other cosolvents is shown to produce novel porous monodisperse poly(divinylbenzene) microspheres. These microspheres have diameters between 4 and 7 μm, total pore volumes of up to 0.52 cm³/g, and surface areas of up to 800 m²/g. As no surfactant nor stabilizer was used in the preparation of these particles, their surfaces are free of any such residues. The particles were slurry-packed into stainless steel columns for size exclusion chromatography evaluation, and the results show an exclusion limit at molecular weights of 500 g/mol. © 1998 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 36: 1543–1551, 1998     

RAFT of sulfobetaine for modifying poly(glycidyl methacrylate) microspheres to reduce nonspecific protein adsorption

The minimization of nonspecific protein adsorption is a crucial step in the development of bioseparation processes, immunoassays, and affinity diagnostics. Among the numerous biomaterials, polyzwitterions are known to effectively suppress protein and cell adhesion. This article describes the formation of monodisperse polymer microspheres coated with polysulfobetaine with the aim to limit nonspecific adsorption of bovine serum albumin (BSA) as a model protein. In this process, 2‐μm poly(glycidyl methacrylate) (PGMA) microspheres were prepared by dispersion polymerization. To render the microspheres hydrophilic and biocompatible, [3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonium hydroxide (MPDSAH) was grafted from the surface by reversible addition‐fragmentation chain transfer (RAFT) polymerization. Elemental analysis of the modified microspheres revealed up to 20 wt % of poly{[3‐(methacryloylamino)propyl]dimethyl(3‐sulfopropyl)ammonimum hydroxide} (PMPDSAH). The microspheres were characterized in terms of particle size, morphology, and zeta potential. The amount of BSA nonspecifically adsorbed on the PMPDSAH‐modified microspheres decreased to half of that captured on the unmodified PGMA microspheres. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2273–2284     

Control of heterogeneous structure of porous polymer microspheres prepared from polymerization system and preformed polymer system

The studies on control of heterogeneous structure of porous polymer microspheres prepared for suspension polymerization system and preformed polymer system in author’s research group were reviewed. Firstly, the phase-separation behavior in O/W suspension polymerization system for preparation of porous poly(divinylbenzene) microspheres was quantitatively studied by combining transmittance and gelation point measurement, from which the morphology can be manipulated. The same method can be employed to study the pore size control in W/O hydrophilic polymerization system. Because the simple porous microsphere could not satisfy new applications, we developed new methods to prepare gigaporous microsphere, which possessed much larger pores than those obtained by general diluents, for chromatographic separation media, as well as hollow-porous microsphere for construction of cell-like microreactor. Furthermore, in order to overcome the difficulty of heterogeneous structure control for preformed polymer system, we developed special methods to obtain porous, hollow-porous, and hollow chitosan microspheres. Finally, some application results by utilizing special morphologies were introduced.     

一步聚合法制备壳核型、可控阶层结构的羰基铁/聚苯乙烯复合微球

采用改进的悬浮聚合法合成了一系列粒径和结构可调的羰基铁粉/聚苯乙烯磁性高分子微球.利用傅立叶变换红外光谱仪、热重分析仪、X射线衍射仪、扫描电镜等分析了微球的结构、化学成分及形貌.结果表明,通过改变苯乙烯单体和聚乙烯醇(PVA)的加入量,可以制备三类不同形貌和结构的复合微球,即多孔复合微球,无孔复合微球和含"带状"突起的...     

Surface modification of thermally expandable microspheres by grafting poly(glycidyl methacrylate) using ARGET ATRP

This study demonstrates the surface modification of thermally expandable core/shell microspheres by grafting glycidyl methacrylate (GMA) using activators regenerated by electron transfer (ARGET) ATRP. To retain the expansion properties it was essential to minimize the shear forces, use solvents compatible with the microspheres and keep the reaction times short (three hours or less). Using microspheres with hydroxyl groups on the surface, it was found that after converting these to α-bromo esters, GMA could be grafted by ARGET ATRP using only 50 ppm of copper catalyst in toluene at 30 °C. Decent control of the polymerization was achieved with PMDETA as ligand reaching PDIs of 1.4 for the solution polymerization of GMA. When microspheres were present, the polymerization was less controlled with higher PDIs. The epoxide groups of the grafted microspheres were hydrolyzed by HCl in THF providing a hydrophilic surface of the microsphere. The expansion property of the microspheres was studied after each reaction step by thermal mechanical analysis, and it was found that the expansion capacity was well preserved with only limited negative effect on the microspheres.     

Nonswellable and swellable ethylene glycol dimethacrylate-acrylic acid copolymer microspheres

In this study, nonswellable and swellable poly(ethylene glycol dimethacrylate/acrylic acid) copolymer microspheres, in the size range of 50–150 μm, were produced by conventional and modified suspension copolymerizations of the respective monomers, i.e., ethyleneglycol dimethacrylate (EGDMA) and acrylic acid (AA) in aqueous media. Poly(vinyl alcohol) and benzoyl peroxide were used as the stabilizer and the initiator. The diluent, i.e., toluene was included in the polymerization recipe of the modified suspension polymerization. The microspheres were characterized by optical microscopy, FTIR, and FTIR-DRS, and potentiometric titrations. Highly crosslinked, transparent, and nonswellable poly(EGDMA/AA) microspheres were obtained with the conventional suspension polymerization procedure. The modified suspension polymerization provided swellable, opaque, and crosslinked copolymer microspheres. Acrylic acid incorporation into the copolymeric microspheres were significantly higher in the modified procedure, relative to the conventional procedure. © 1996 John Wiley & Sons, Inc.     

Preparation and characterization of core-shell polystyrene/polychloromethylstyrene and hollow polychloromethylstyrene micrometer-sized particles of narrow-size distribution

Polystyrene core microspheres of narrow-size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2-methoxy ethanol. Polystyrene/polychloromethylstyrene and polystyrene/poly(chloromethylstyrene-divinylbenzene) core-shell microspheres of narrow-size distribution were prepared by seeded emulsion polymerization of chloromethylstyrene or chloromethylstyrene and divinylbenzene in the presence of the polystyrene core microspheres at 71 °C. Core-shell particles with different properties (size, surface morphology, and composition) have been prepared by changing various parameters belonging to the emulsion polymerization process, e.g., volume of the chloromethylstyrene and the volume ratio of chloromethylstyrene to divinylbenzene. Dissolution of the polystyrene core of the polystyrene/poly(chloromethylstyrene-divinylbenzene) core-shell particles resulted in the formation of crosslinked hollow polychloromethylstyrene microspheres, broken crosslinked polychloromethylstyrene shells, or particles containing voids, depending on the composition of the polystyrene/poly(chloromethylstyrene-divinylbenzene) particles.