Effect of GMA on monodisperse epoxy‐functionalized polymer microsphere particles by dispersion copolymerization of styrene with glycidyl methacrylate

Monodisperse poly[styrene‐co‐glycidyl methacrylate (GMA)] microparticles were synthesized by dispersion copolymerization in a water–ethanol medium. The effects of various polymerization parameters on the particle size and size distribution of the dispersion copolymerization were investigated. The dispersion of polymer particles decreased when the GMA was added if the polystyrene homopolymer particles were polydispersed. The GMA acted as a comonomer as well as a costabilizer in the dispersion copolymerization of styrene with GMA. The solvency of the monomer increased with the concentration of GMA in the polymerization medium because GMA has a greater hydrophilicity than styrene, resulting in a large particle size and a slow polymerization rate. From an HCl–dioxane analysis of the poly(styrene‐co‐GMA) microparticles, great amounts of epoxy groups were detected after the completion of dispersion copolymerization. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1206–1212, 2001     

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.     

Synthesis of poly(styrene‐co‐4‐vinylpyridine) microspheres via dispersion polymerization: Effect of the concentration of 4‐vinylpyridine

Amphiphilic copolymer microspheres of poly(styrene‐co‐4‐vinylpyridine) were prepared by dispersion polymerization in an alcohol/water medium. The synthesis of poly(styrene‐co‐4‐vinylpyridine) microparticles was successfully carried out, and the latexes had a spherical morphology with good monodispersity. The degree of conversion in the early stage of polymerization decreased with increasing 4‐vinylpyridine (4VP) monomer content, but the final conversions were similar (>95%). The copolymerization rate decreased with increasing 4VP content, and a broad particle size distribution was observed with 20 wt % 4VP because of the prolonged nucleation time. With the 4VP concentration increasing, the molecular weight of the copolymer microspheres decreased, and the glass‐transition temperature of the copolymers increased; this indicated that all the copolymers were random and homogeneous. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

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     

Study of multi‐monomer melt‐grafting onto polypropylene in an extruder

Free‐radical melt‐grafting of the dual‐monomer systems glycidyl methacrylate–styrene (GMA‐St) and hydroxyethyl methacrylate–styrene (HEMA‐St) onto polypropylene (PP) has been studied using a single‐screw extruder. For single monomer grafting systems, degradation of PP was unavoidable and deterioration of the mechanical properties of the grafted PP subsequently occurred because of β‐scission of PP chains during the free‐radical melt‐grafting process. However, for the dual‐monomer systems, it is shown that the addition of styrene as a comonomer can significantly enhance the GMA or HEMA grafting levels on PP and reduce the extent of β‐scission of PP backbone. It has been found that the grafting degree of dual‐monomer melt‐grafted PP, such as PP‐g‐(GMA‐co‐St) or PP‐g‐(HEMA‐co‐St), is about quadruple that of single‐monomer grafted PP for the same monomer and dicumyl peroxide concentrations. Moreover, the melt flow rate of the dual‐monomer grafted PP is smaller than that of the unmodified PP. Hence, PP not only was endowed with higher polarity, but also kept its good mechanical properties. © 2000 Society of Chemical Industry     

Environmentally benign precipitation copolymerization of methacrylate ester and styrene to make polymeric microspheres in supercritical carbon dioxide

The polymeric microspheres were synthesized by the precipitation copolymerization of glycidyl methacrylate (GMA) with methacrylic acid(MAA) or 2‐hydoxyethyl methacrylate (2‐HEMA) containing styrene (ST) in SC‐CO₂. Scanning electron microscopy (SEM) showed that the products were spherical microparticles, with the addition of MAA and/or 2‐HEMA as the monomer, with diameter of 0.2–2 μm. The effects of copolymerization pressure, temperature, and ratios of GMA/MAA, ST, and/or GMA/2‐HEMA, on the particle size and morphology were investigated in detail. A new experiment setup is proposed for the large amount of production, based on the rule of lower monomer concentration, more stable system, and better use of the present polymerization apparatus. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2425–2431, 2007     

Lamotrigine‐loaded polyacrylate nanoparticles synthesized through emulsion polymerization

A series of copolymeric nanoparticles of the partially water‐soluble monomer ethyl methacrylate and the water‐soluble monomer 2‐hydroxyl ethyl methacrylate were synthesized from emulsions containing sodium dodecyl sulfate via free‐radical polymerization. Lamotrigine, as a model drug, was loaded in nanoparticles during in situ polymerization. A stable and transparent poly(ethyl methacrylate‐co‐hydroxyl ethyl methacrylate) nanolatex was produced for all compositions and characterized for particle size by dynamic light scattering and transmission electron microscopy. Particles were found to be smaller than 50 nm in size. Structural characterization of copolymers was done by infrared spectrometry, gel permeation chromatography, and NMR spectroscopy. Drug encapsulation efficiency was determined by ultraviolet (UV)–visible spectrometry and was found to be 26–62% for copolymers with different compositions. UV data suggest molecular‐level dispersion of the drug in the nanoparticles. In vitro drug‐release studies showed the controlled release of lamotrigine. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation of monodisperse fluorescent core–shell polymer microspheres with functional groups in the shell layer by two‐stage distillation–precipitation polymerization

Monodisperse crosslinked core–shell micrometer‐sized microspheres bearing a brightly blue fluorescent dye, carbazole, and containing various functional groups in the shell layers were prepared by a two‐stage distillation–precipitation polymerization in acetonitrile in the absence of any stabilizer. Commercial divinylbenzene (DVB), containing 80 vol.% of DVB, was polymerized by distillation–precipitation in acetonitrile without any stabilizer using 2,2′‐azobisisobutyronitrile (AIBN) as the initiator for the first stage of polymerization which resulted in monodisperse polyDVB microspheres used as the core. Several functional monomers, including 2‐hydroxyethyl methacrylate and acrylonitrile together with N‐vinylcarbazole blue fluorescent comonomer, were incorporated into the shell layers with AIBN as initiator during the second stage of polymerization. The resultant core–shell polymer microspheres were characterized using scanning electron microscopy, Fourier transform infrared spectroscopy, UV‐visible spectroscopy and fluorescence spectroscopy. Copyright © 2006 Society of Chemical Industry     

Stable poly(glycidyl methacrylate‐co‐ethylene glycol dimethacrylate) microspheres via precipitation polymerization

Narrow‐dispersion or monodisperse with stable and smooth surface polymer microspheres were prepared without a significant coagulum by precipitation polymerization in the absence of any stabilizer. The monomer glycidyl metharylate (GMA) was copolymerized with ethyleneglycol dimethacrylate (EGDMA) as crosslinker by precipitation polymerization technique with 2,2′‐azobisisobutyronitrile as initiator in neat acetonitrile. The effects of the content of EGDMA on the polymerization characteristics and size/uniformity of the microspheres were investigated. The onset of the thermal degradation temperature at higher temperature and the swelling test suggest that the prepared particles were highly crosslinked. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Electrooptical‐responsive microsphere with ferroelectric liquid crystalline segments

We synthesized a ferroelectric liquid crystalline monomer (4‐[4′‐(7‐octeneloxy)benzoyloxy]benzoate‐2‐methylbutyester, OBBM) possessing both carboxyl p‐benzolxybenzoate and carboxyl (s)‐(‐)‐2‐methylbutylester as a mesogenic group in its side chain. The liquid crystalline and styrene monomers were employed to make matrices of microspheres prepared by dispersion, suspension, or emulsion polymerization. In this study, we investigated, in detail, physicochemical properties, thermal responses, and electrooptical responses of the microspheres possessing liquid crystalline abilities. The ferroelectric liquid crystalline monomer OBBM had a thermotropic liquid crystalline ability, two‐phase transition temperatures, and a Smectic C* texture, which is characteristic of ferroelectric liquid crystalline substances. The microspheres prepared also exhibited a liquid crystalline ability, and the phase‐transition temperatures toward the liquid crystalline segments into the microspheres prepared by copolymerizing the liquid crystalline and styrene monomers could be decreased with increasing of the styrene monomer. Furthermore, we found that the microspheres remarkably exhibited electrooptical responses at about 8 V. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 81: 2490–2499, 2001     

Preparation of polymer‐supported polyethylene glycol and phase‐transfer catalytic activity in benzoate synthesis

The crosslinked polymeric microspheres (GMA/MMA) of glycyl methacrylate (GMA) and methyl methacrylate (MMA) were prepared by suspension polymerization. Polyethylene glycol (PEG) was grafted on GMA/MMA microsphers via the ring‐opening reaction of the epoxy groups on the surfaces of GMA/MMA microspheres, forming a polymer‐supported triphase catalyst, PEG‐GMA/MMA. The Phase‐transfer catalytic activity of PEG‐GMA/MMA microspheres was evaluated using the esterification reaction of n‐chlorobutane in organic phase and benzoic acid in water phase as a model system. The effects of various factors on the phase transfer catalysis reaction of liquid–solid–liquid were investigated. The experimental results show that the PEG‐GMA/MMA microspheres are an effective and stable triphase catalyst for the esterification reaction carried out between oil phase and water phase. The polarity of the organic solvent, the ratio of oil phase volume to water phase volume and the density of the grafted PEG on PEG‐GMA/MMA microspheres affect the reaction rate greatly. For this investigated system, the solvent with high polarity is appropriate, an adequate volume ratio of oil phase to water phase is 2:1, and the optimal PEG density on the polymeric microspheres is 15 g/100 g. Triphase catalysts offer many advantages associated with heterogeneous catalysts such as easy separation from the reaction mixture and reusability. The activity of PEG‐GMA/MMA microspheres is not nearly decreased after reusing of 10 recycles. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Preparation of micron‐size monodispersed PS/P(St/MAA) microspheres by seeded dispersion polymerization

Uniform polystyrene (PSt) particles with the size of 1.9 μm were first prepared via dispersion polymerization, and then used as the seeds in a second‐stage dispersion copolymerization of styrene (St) and methacrylic acid (MAA) to produce carboxyl‐carrying microspheres. The PSt seed particles were swollen by monomer mixture of St and MAA, including an oil‐soluble initiator 2,2′‐azobisiso‐butyronitrile (AIBN), before polymerization. Finally, uniform PS/P(St/MAA) (polydispersity index, PDI = 1.02) microspheres with the size of 2.2 μm were obtained. The average particle size and size distribution of the final microspheres were investigated. MAA contents between 54 and 97 mg/g were detected from the PS/P(St/MAA) particles produced under different conditions. Dispersion medium has great influence on the kinetics of polymerization, due to its effect on the partitioning of monomers, solvents, and initiator in the particle phase, probably as well as on the conformation of the dispersion agent on the surface of the particles. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 99: 3586–3591, 2006     

Synthesis and characterization of rutile titanium dioxide/polyacrylate nanocomposites for applications in ultraviolet light‐shielding materials

Rutile titanium dioxide (TiO₂)/poly(methyl methacrylate‐acrylic acid‐butyl acrylate) nanocomposites were synthesized via seeded emulsion polymerization and characterized by Fourier transmission infrared, dynamic light scattering, X‐ray diffraction, ultraviolet–visible (UV–vis) spectroscopy, scanning electron microscopy, transmission electron microscopy, and thermogravimetric analysis to study their UV‐shielding property. The effects of the nanoseed types, surfactant concentrations, and functional monomer amounts on the polymerization conversion, particle size, emulsion stability, and morphologies of the resulting nanocomposites were investigated. The dependence of UV‐shielding performance on the nanoparticle content and dispersion was also explored. The optimized results are obtained with 2 wt% of TiO₂ nanoparticles addition, and the effectiveness of UV shielding is significantly increased by using the synthesized rutile nano‐TiO₂/polyacrylates, for which the nanocomposite coating with a thickness of 200 μm could block up to 99.99% of UV light (≤350 nm) as confirmed by UV–vis spectrometry. POLYM. COMPOS., 36:8–16, 2015. © 2014 Society of Plastics Engineers     

Preparation and characterization of micron‐sized magnetic microspheres by one‐step suspension polymerization

Micron‐sized magnetic microspheres with different functional groups were prepared by one‐step suspension copolymerization of styrene, divinyl benzene, and methyl methacrylate in the presence of oleic acid‐coated magnetic nanoparticles. In the present work, we used benzoyl peroxide as an initiator and poly(vinyl alcohol) (PVA‐1788; degree of polymerization: 1,700; degree of hydrolysis: 88%) as a stabilizer. We also added acrylamide (AM) monomer in the aqueous phase and methacrylic acid (MAA) in the oil phase. The morphology and properties of the resulting magnetic microspheres were examined by optical micrographs (OMs), vibrating‐sample magnetometer (VSM), and Fourier transform infrared spectrometer (FT IR). The results showed the three products have uniform and spherical form with superparamagnetism and well dispersion. Moreover, we found that monomer AM had a little contribution to the copolymerization, and MAA could strikingly decrease the diameter of the final microspheres. The magnetic microspheres with functional groups could be linked well with the IgG‐FITC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

A New Strategy to Prepare Poly(2‐methyl‐2‐oxazoline)‐Based Antifouling Coatings: Using UV‐Crosslinked Copolymer Anchors

A series of the copolymer, poly(styrene‐random‐glycidyl methacrylate) (P(St‐r‐GMA)), is synthesized by free radical polymerization, and characterized by ¹H NMR spectroscopy and gel permeation chromatography. The various substrates are then modified by P(St‐r‐GMA) under ultraviolet (UV) irradiation. Subsequently, the poly(2‐methyl‐2‐oxazoline) (PMOXA) based coatings are prepared by anchoring amino‐terminated PMOXA onto the P(St‐r‐GMA) modified surfaces through the reaction between the amino group of PMOXA and epoxy group of P(St‐r‐GMA). The results of ellipsometry, X‐ray photoelectron spectroscopy, atomic force microscopy, and water contact angle reveal that PMOXA‐based coatings can be prepared successfully on the substrates through UV‐crosslinked P(St‐r‐GMA) as anchoring coatings. Besides, the PMOXA‐based coatings display not only a superior antifouling property but long‐term stability as well. Furthermore, the location of the coating formed on the substrate can be well controlled through selecting the site of UV irradiation, which can be utilized for the selectivity of protein adsorption (or resistance) on special devices.     

RAFT‐mediated graft polymerization of glycidyl methacrylate in emulsion from polyethylene/polypropylene initiated with γ‐radiation

The successful reversible addition‐fragmentation (RAFT)‐mediated graft polymerization of glycidyl methacrylate (GMA) in emulsion phase from polyethylene/polypropylene nonwoven fabric using 4‐cyano‐4‐[(phenylcarbonothioyl)thio]pentanoic acid under γ‐irradiation at ambient condition is reported. While conventional graft polymerization in emulsion phase yielded grafted materials with low of grafting (Dg) values [<7.5% at 10% (wt/wt) GMA], addition of RAFT agent to the graft polymerization system allowed the synthesis of polyethylene/polypropylene‐g‐poly(GMA) with more tunable Dg (8% ≤ Dg ≤ 94%) by controlling the grafting parameters. Relatively good control (PDI ～1.2 for selected grafting conditions) during polymerization was attained at 100:1 monomer‐to‐RAFT agent molar ratio. The number average molecular weight of free poly(glycidyl methacrylate) (PGMA) increased as a function of monomer conversion. NMR analyses of the free PGMA homopolymers indicate the presence of dithiobenzoate group from 4‐cyano‐4‐((phenylcarbonothioyl)thio) pentanoic acid on the polymer chain. The reactive pendant oxirane group of the grafted GMA can be modified for various environmental and industrial applications. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45270.     

Preparation and characterization of imidazole‐functionalized microspheres

The preparation of imidazole‐functionalized latex microspheres by a two‐stage emulsion copolymerization process and their characterization are reported on. Emulsifier‐free emulsion copolymerization of styrene (St) and 1‐vinyl imidazole (VIMZ) exhibited bimodal particle size distributions caused by secondary homogeneous nucleation process. However, secondary nucleation can be avoided by using cetyltrimethylammonium bromide (CTAB) as a stabilizer at a concentration below its cmc (critical micelle concentration). This would result in the formation of monodisperse latex particles. The final particle size diameter depended on the concentration of CTAB as well as the amount of VIMZ. To control the amount of the functional imidazole groups on the latex particle surfaces, independent of the latex diameters, without secondary nucleation of particles, the seeded emulsion copolymerization of styrene and VIMZ was explored as a second‐stage polymerization at different concentrations and ratios of monomers in the presence of the previously prepared monodisperse poly(styrene‐co‐1‐vinyl imidazole) seed latex particles. The concentration of imidazole functional groups on the surface of the latex particles could also be varied through the rearrangement of hydrophilic imidazole groups by varying the second‐stage monomer addition process such as the utilization of monomer‐swollen seed particles or a shot addition of monomers. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 120:5753–5762, 2006     

One‐pot synthesis of self‐stabilized and carboxyl‐functionalized fluorescent poly(methyl methacrylate) microspheres covalently dyed with tris(8‐hydroquinolinato)aluminium by dispersion polymerization

The dispersion polymerization of methyl methacrylate (MMA) with fluorescent monomer tris[2‐((8‐hydroxyquinolin‐5‐yl)methoxy)ethyl methacrylate]aluminium (Al‐HQHEMA) was investigated to obtain fluorescent microspheres under varying conditions (such as composition of dispersion medium, and content of stabilizer polyvinylpyrrolidone (PVP) and Al‐HQHEMA) in methanol–water at 70 °C with 2,2′‐azoisobutyronitrile as the initiator. Fluorescent microspheres with particle size of 2.039 µm and uniformity of 0.171 were obtained under the following conditions: methanol–water, 7:3 (v/v); PVP, 15 wt% of MMA; Al‐HQHEMA solution, 1.5 mL. Maleic monoester of monomethoxyl poly(ethylene glycol) (Mal‐MPEG) was used as a comonomer to simultaneously incorporate carboxyl groups and PEG chains. With Mal‐MPEG, no aggregation was observed in the measurements of particle size and size distribution for the obtained microspheres after cleaning off PVP, indicating that self‐stabilized fluorescent microspheres were obtained. While without Mal‐MPEG, obvious aggregation was observed. The determination of surface carboxyl content using aqueous acid–base titration showed that most of the carboxyl groups of Mal‐MPEG were located on the surface of the microspheres. © 2015 Society of Chemical Industry     

Immobilization of Candida lipolytica lipase on macroporous beaded terpolymers with epoxy groups

A series of macroporous beaded terpolymers with epoxy groups were synthesized by suspension polymerization with glycidyl methacrylate (GMA), ethylene glycol dimethacrylate (EGDMA), and the third monomers including styrene, methyl methacrylate, n‐butyl acrylate (BA), butyl methacrylate (BMA), and 2‐hydroxyethyl methacrylate for immobilization of Candida lipolytica lipase. The effect of various third monomers on loading and activity recovery of immobilized lipase were studied. Terpolymers with BA as the third monomer were found to give the biggest loading of lipase, and the activity recovery of lipase immobilized on poly(GMA‐EGDMA‐BA) terpolymers reached 79.0%. As the content of BA (%) increasing, the loading of lipase enhanced, but the activity recovery reached 88.5% for the initial stage and decreased to 46.9% at last. The poly(GMA‐EGDMA‐BA‐10) showed an optimal result in lipase immobilization. Lipase immobilized on poly(GMA‐EGDMA‐BA‐10) carriers had broader pH and higher temperature stability. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Preparation of uniform poly(glycidyl methacrylate) porous microspheres by membrane emulsification–polymerization technology

Uniform poly(glycidyl methacrylate‐divinyl‐benzene) (P(GMA‐DVB)) and poly(glycidyl methacrylate‐ethylene dimethacrylate) (P(GMA‐EGDMA)) porous microspheres with several 10 μm were successfully prepared by membrane emulsification–polymerization technology. Conventional suspension polymerization method was first investigated by examining the effects of recipe components on the morphologies of P(GMA‐DVB), including stabilizer, diluent, and crosslinker to select a optimum recipe. The membrane emulsification–polymerization process was developed to prepare uniform PGMA porous microspheres as the following: the oil phase composed of monomer, diluent and initiator was pressed through membrane pores into the aqueous phase to form uniform droplets, and subsequent suspension polymerization was carried out. GMA and 4‐methyl‐2‐pentanol in the selected recipe were relatively hydrophilic, and therefore oil phase could wet the hydrophilic glass membrane and bring about polydispersed droplets. However, when isooctane was added as a component of diluents, the uniform droplets could be prepared by membrane emulsification method. In the membrane emulsification–polymerization, the coagulation between microspheres obviously decreased while yield of microspheres slightly increased. To extend the application of PGMA, as a trail, uniform P(GMA‐EGDMA) porous microspheres were also successfully prepared by membrane emulsification–polymerization with a isooctane contained diluent, even though EGDMA was more hydrophilic than DVB. Therefore, recipe was found the important factor to prepare uniform PGMA porous microspheres using membrane emulsification–polymerization method. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5018–5027, 2006