Magnetic poly(glycidyl methacrylate) microspheres prepared by dispersion polymerization in the presence of electrostatically stabilized ferrofluids

Fine magnetite nanoparticles, both electrostatically stabilized and nonstabilized, were synthesized in situ by precipitation of Fe(II) and Fe(III) salts in alkaline medium. Magnetic poly(glycidyl methacrylate) (PGMA) microspheres with core‐shell structure, where Fe₃O₄ is the magnetic core and PGMA is the shell, were obtained by dispersion polymerization initiated with 2,2′‐azobisisobutyronitrile (AIBN), 4,4′‐azobis(4‐cyanovaleric acid) (ACVA), or ammonium persulfate (APS) in ethanol containing poly(vinylpyrrolidone) or ethylcellulose stabilizer in the presence of iron oxide ferrofluid. The average microsphere size ranged from 100 nm to 2 μm. The effects of the nature of ferrofluid, polymerization temperature, monomer, initiator, and stabilizer concentration on the PGMA particle size and polydispersity were studied. The particles contained 2–24 wt % of iron. AIBN produced larger microspheres than APS or ACVA. Polymers encapsulating electrostatically stabilized iron oxide particles contained lower amounts of oxirane groups compared with those obtained with untreated ferrofluid. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5827–5837, 2004     

Preparation of nanoparticles of double‐hydrophilic PEO‐PHEMA block copolymers by AGET ATRP in inverse miniemulsion

Atom transfer radical polymerization with activators generated by electron transfer initiating/catalytic system (AGET ATRP) of 2‐hydroxyethyl methacrylate (HEMA) was carried out in inverse miniemulsion. Water‐soluble ascorbic acid as a reducing agent and mono‐ and difunctional poly(ethylene oxide)‐based bromoisobutyrate (PEO‐Br) as a macroinitiator were used in the presence of CuBr₂/tris[(2‐pyridyl)methyl]amine (TPMA) and CuCl₂/TPMA complexes. The use of poly(ethylene‐co‐butylene)‐block‐poly(ethylene oxide) as a polymer surfactant resulted in the formation of stable HEMA cyclohexane inverse dispersion and PHEMA colloidal particles. All polymerizations were well‐controlled, allowing for the preparation of well‐defined PEO‐PHEMA and PHEMA‐PEO‐PHEMA block copolymers with relatively high molecular weight (DP > 200) and narrow molecular weight distribution (M_w/M_n < 1.3). These block copolymers self‐assembled to form micellar nanoparticles being 10–20 nm in diameter with uniform size distribution, and aggregation number of ～10 confirmed by atomic force microscopy and transmission electron microscopy. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4764–4772, 2007     

Magnetic poly(2‐hydroxyethyl methacrylate‐co‐ethylene dimethacrylate) microspheres by dispersion polymerization

Crosslinked poly(2‐hydroxyethyl methacrylate)‐based magnetic microspheres were prepared in a simple one‐step procedure by dispersion polymerization in the presence of several kinds of iron oxides. Cellulose acetate butyrate and dibenzoyl peroxide were used as steric stabilizer and polymerization initiator, respectively, and ethylene dimethacrylate was a crosslinking agent. The resulting product was characterized in terms of particle size, particle size distribution, iron(III) content, and magnetic properties. In the presence of needle‐like maghemite in the polymerization mixture and under suitable conditions, magnetic microspheres with relatively narrow size distribution were formed. An increase in the particle size and, at the same time, a decrease in molecular weight of uncrosslinked polymers resulted, as the continuous phase became richer in 2‐methylpropan‐1‐ol. Coercive force of needle‐like maghemite‐containing particles was higher than that of cubic magnetite‐loaded microspheres. Coercive force increased with the decreasing iron content in the particles. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1161–1171, 2000     

Synthesis and characterization of spherical and hemispherical polyepoxide micrometer‐sized particles of narrow size distribution by a single‐step swelling of uniform polystyrene template microspheres with glycidyl methacrylate

Polystyrene template microspheres of narrow size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2‐methoxy ethanol. Spherical and hemispherical polystyrene/poly(glycidyl methacrylate) microspheres of narrow size distribution were prepared by a single‐step swelling of the polystyrene template microspheres with the swelling solvent monomer glycidyl methacylate, followed by polymerization of the monomer within the swollen template microspheres at 73 °C. Uniform polystyrene/poly(glycidyl methacylate‐ethylene glycol dimethacrylate) polyepoxide composite microspheres were synthesized similarly, substituting glycidyl methacylate for glycidyl methacylate and ethylene glycol dimethacrylate. Uniform crosslinked poly(glycidyl methacylate‐ethylene glycol dimethacrylate) polyepoxide microspheres have been prepared by dissolution of the PS template polymer of the former composite microspheres. Particles with different properties, for example size, size distribution, shape, surface morphology, surface area, and so forth, were prepared by changing various parameters belonging to the swelling and/or polymerization steps, for example, volume of the swelling monomer/s and/or the swelling solvent dibutyl phthalate. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4612–4622, 2007     

Self‐Initiated Photopolymerization and Photografting of Acrylic Monomers

Summary: This work demonstrates that acrylic acid (AA), glycidyl acrylate (GA) and several other acrylic monomers can be photopolymerized and photografted onto high‐density polyethylene (HDPE) by self‐initiation. The self‐initiation mechanism of these acrylic monomers is possibly by an excitation of the monomer to a triplet state (T₃) with enough energy to abstract hydrogen from the polymer substrate and initiate the grafting.

Grafting conversion of acrylic acid (AA), methacrylic acid (MAA), 2‐hydroxyethyl acrylate (HEA), glycidyl acrylate (GA), 2‐hydroxyethyl methacrylate (HEMA) and poly(ethylene glycol) methacrylate (PEGMA) as a function of irradiation time.     

Graft copolymers of polyethylene by atom transfer radical polymerization

Poly(ethylene‐g‐styrene) and poly(ethylene‐g‐methyl methacrylate) graft copolymers were prepared by atom transfer radical polymerization (ATRP). Commercially available poly(ethylene‐co‐glycidyl methacrylate) was converted into ATRP macroinitiators by reaction with chloroacetic acid and 2‐bromoisobutyric acid, respectively, and the pendant‐functionalized polyolefins were used to initiate the ATRP of styrene and methyl methacrylate. In both cases, incorporation of the vinyl monomer into the graft copolymer increased with extent of the reaction. The controlled growth of the side chains was proved in the case of poly(ethylene‐g‐styrene) by the linear increase of molecular weight with conversion and low polydispersity (M_w /M_n < 1.4) of the cleaved polystyrene grafts. Both macroinitiators and graft copolymers were characterized by ¹H NMR and differential scanning calorimetry. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2440–2448, 2000     

Supertoughness and critical interparticle distance dependence in poly(butylene terephthalate) and poly(ethylene‐co‐glycidyl methacrylate) blends

Supertough poly(butylene terephthalate) (PBT)‐based blends were obtained by the melt blending of PBT with 0–30 wt % poly(ethylene‐co‐glycidyl methacrylate) (EGMA). The reaction between PBT and EGMA was detected by torque measurements. The particle size was almost constant with increasing EGMA content, and this indicated that compatibilization occurred. The minimum EGMA content for achieving supertoughness (i.e., an impact strength 16 times greater than that of PBT) was 20 wt %. The interparticle distance was the parameter controlling toughness in these PBT/EGMA blends. The dependence of the critical interparticle distance (τ_c) on the modulus of the dispersed phase appeared only at low τ_c values, and the primary dependence of τ_c on the ratio of the modulus of the matrix to the modulus of the rubbery dispersed phase was proposed. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 2236–2247, 2003     

Effects of the reaction parameters on the properties of thermosensitive poly(N‐isopropylacrylamide) microspheres prepared by precipitation and dispersion polymerization

Poly(N‐isopropylacrylamide) (PNIPAAm)‐based microspheres were prepared by precipitation and dispersion polymerization. The effects of several reaction parameters, such as the type and concentration of the crosslinker (N,N′‐methylenebisacrylamide or ethylene dimethacrylate), medium polarity, concentration of the monomer and initiator, and polymerization temperature, on the properties were examined. The hydrogel microspheres were characterized in terms of their chemical structure, size and size distribution, and morphological and temperature‐induced swelling properties. A decrease in the particle size was observed with increasing polarity of the reaction medium or increasing concentration of poly(N‐vinylpyrrolidone) as a stabilizer in the dispersion polymerization. The higher the content was of the crosslinking agent, the lower the swelling ratio was. Too much crosslinker gave unstable dispersions. Although the solvency of the precipitation polymerization mixture controlled the PNIPAAm microsphere size in the range of 0.2–1 μm, a micrometer range was obtained in the Shellvis 50 and Kraton G 1650 stabilized dispersion polymerizations of N‐isopropylacrylamide in toluene/heptane. Typically, the particles had fairly narrow size distributions. Copolymerization with the functional glycidyl methacrylate monomer afforded microspheres with reactive oxirane groups. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 968–982, 2006     

Dispersion polymerization accompanied by CO2 fixation: Synthesis of particles of polymers bearing cyclic carbonate and epoxide moieties

Radical dispersion polymerization of glycidyl methacrylate accompanied by CO₂ fixation yielded particles of polymers bearing cyclic carbonate and epoxide moieties in the presence of polymeric dispersion stabilizers. Cellulose acetate successfully stabilized the dispersion, whereas poly(N‐vinylpyrrolidone) did not. Spherical particles with diameters of 1–10 μm could be prepared under the optimized conditions. The epoxide moieties in the particle were hydrolyzed selectively keeping the shapes of the particles. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Understanding and preventing the formation of deformed polymer particles during synthesis by a seeded polymerization method

Uniformly sized porous polymer particles with different polarity namely poly(divinylbenzene), poly(vinyl acetate‐co‐divinylbenzene), poly(ethylene dimethacrylate), and poly (glycidyl methacrylate‐co‐ethylene dimethacrylate) were prepared in the micron‐size range by a seeded polymerization method. Parameters affecting the particle morphologies including monomer mixture content, porogen content, and polystyrene (PS) seed latexes were varied, and the morphologies of the resulting particles were investigated by scanning electron and confocal microscopy. The results obtained indicated that the particle shape depended dominantly on the molecular weight of the PS seed template. Deformed particles, including collapsed spheres and spheres with holes were obtained when high molecular weight PS seeds were used, whereas well‐defined polymer particles were produced easily by using low molecular weight seeds. The use of 1,1‐diphenylethylene as a chain terminator during seed polymerization is proposed in this work as an efficient method to lower molecular weight of PS in seed particles while keeping seed size small. This low molecular weight seed template retained its spherical geometry after swelling and polymerization with different second stage monomers. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Encapsulation of nanomaterials using an intermediary layer cross‐linkable ABC triblock copolymer

For the preparation of core‐shell nanoparticles containing functional nanomaterials, a photo‐cross‐linkable amphiphilic ABC triblock copolymer, poly(ethylene glycol)‐b‐poly(2‐cinnamoyloxyethyl methacrylate)‐b‐poly(methyl methacrylate) (PEG‐PCEMA‐PMMA), was synthesized. This triblock copolymer was then used to encapsulate Au nanoparticles or pyrene. The triblock copolymer of PEG‐b‐poly(2‐hydroxyethyl methacrylate)‐b‐PMMA (PEG‐PHEMA‐PMMA) (M_n = 15,800 g/mol, M_w/M_n = 1.58) was first synthesized by activators generated by electron transfer atom transfer radical polymerization. Its middle block was then functionalized with cinnamoyl chloride. The degrees of polymerization of the PEG, PHEMA, and PMMA blocks were 45, 13, and 98, respectively. PMMA‐tethered Au nanoparticles (with an average diameter of 3.0 nm) or pyrene was successfully encapsulated within the PEG‐PCEMA‐PMMA micelles. The intermediary layers of the micelles were then cross‐linked by UV irradiation. The spherical structures of the PEG‐PCEMA‐PMMA micelles containing Au nanoparticles or pyrene were not changed by the photo‐cross‐linking process and they showed excellent colloidal stability. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4963–4970, 2009     

Surface molecularly imprinted magnetic microspheres for the recognition of albumin

A new approach, combining metal coordination with the molecular imprinting technique, was developed to prepare affinity materials. Magnetic poly(glycidyl methacrylate) microspheres in monosize form were used for specific recognition toward the target protein. The magnetic poly(glycidyl methacrylate) microspheres were prepared by dispersion polymerization in the presence of magnetite nanopowder. Surface imprinted magnetic poly(glycidyl methacrylate) microspheres based on metal coordination were prepared and used for the selective recognition of human serum albumin. Iminodiacetic acid was used as the metal coordinating agent and human serum albumin was anchored by Cu²⁺ ions on the surface of magnetic poly(glycidyl methacrylate) microspheres by metal coordination. The magnetic poly(glycidyl methacrylate) microspheres were coated with a polymer formed by condensation of tetraethyl orthosilicate and 3‐aminopropyltrimethoxysilane. The human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres were characterized by scanning electron microscopy, attenuated total reflectance Fourier transform infrared spectroscopy and particle size analysis. The maximum adsorption capacity of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres was 37.7 mg/g polymer at pH 6.0. The selectivity experiments of human serum albumin imprinted magnetic poly(glycidyl methacrylate) microspheres prepared with different concentrations in the presence of lysozyme, bovine serum albumin and cytochrome C were performed in order to determine the relative selectivity coefficients.     

Magnetic polyglycidylmethacrylate microspheres by dispersion polymerization

Composite polyglycidylmethacrylate [poly(GMA)] spherical microparticles capable of responding to magnetic fields were prepared by dispersion polymerization of GMA in the presence of iron oxides. The polymerization reaction was carried out in aqueous alcoholic media (methanol, ethanol, propan‐1‐ol, and butan‐1‐ol) using poly‐(N‐vinylpyrrolidone) and 2,2′‐azobisisobutyronitrile as a steric stabilizer and initiator, respectively. Quaternary ammonium salt (Aliquat 336) acting as an electrostatic costabilizer favorably affected dispersity. The solubility parameter of the reaction mixture determined the size of the resulting microspheres. In addition to the particle size distribution, the addition of iron oxide to the polymerization medium also caused a shift of the particle size to higher values. The results show that poly(GMA) particles contained up to 25 wt % iron oxide. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3707–3715, 2001     

Semi‐micro reversed‐phase liquid chromatography for the separation of alkyl benzenes and proteins exploiting methacrylate‐ and polystyrene‐based monolithic columns

Monolithic columns were synthesized inside 1.02 mm internal diameter fused‐silica lined stainless‐steel tubing. Styrene and butyl, hexyl, lauryl, and glycidyl methacrylates were the functional monomers. Ethylene glycol dimethacrylate and divinylbenzene were the crosslinkers. The glycidyl methacrylate polymer was modified with gold nanoparticles and dodecanethiol (C₁₂). The separation of alkylbenzenes was investigated by isocratic elution in 60:40 v/v acetonitrile/water. The columns based on polystyrene‐co‐divinylbenzene and poly(glycidyl methacrylate)‐co‐ethylene glycol dimethacrylate modified with dodecanethiol did not provide any separation of alkyl benzenes. The poly(hexyl methacrylate)‐co‐ethylene glycol dimethacrylate and poly(lauryl methacrylate)‐co‐ethylene glycol dimethacrylate columns separated the alkyl benzenes with plate heights between 30 and 60 μm (50 μL min^?1 and 60°C). Similar efficiency was achieved in the poly(butyl methacrylate)‐co‐ethylene glycol dimethacrylate column, but only at 10 μL min^?1 (0.22 mm s^?1). Backpressures varied from 0.38 MPa in the hexyl methacrylate to 13.4 MPa in lauryl methacrylate columns (50 μL min^?1 and 60°C). Separation of proteins was achieved in all columns with different efficiencies. At 100 μL min^?1 and 60°C, the lauryl methacrylate columns provided the best separation, but their low permeability prevented high flow rates. Flow rates up to 500 μL min^?1 were possible in the styrene, butyl and hexyl methacrylate columns.     

Controlled radical polymerization of 2‐hydroxyethyl methacrylate initiated by photofunctional 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid

We demonstrated that density functional theory calculations provide a reliable and quantitative prediction of the trends in C? S bond dissociation energies using several model compounds as photoinitiator. On the basis of this information, we designed a possible photofunctional initiator for the polymerization of hydrophilic vinyl monomers. Photopolymerization of 2‐hydroxyethyl methacrylate (HEMA) hydrophilic monomer was carried out in ethanol initiated by 2‐(N,N‐diethyldithiocarbamyl)isobutyric acid (DTCA) under UV irradiation. We performed the first‐order time‐conversion plots in this polymerization system, and the straight line in the semilogarithmic coordinates indicated first order in monomer. The molecular weight of the poly(2‐hydroxyethyl methacrylate) (PHEMA) increased with increasing conversion. The molecular weight distribution (M_w/M_n) of the PHEMA was about 1.5. Methyl methacrylate (MMA) could also be polymerized in a living fashion with such a PHEMA precursor as a macroinitiator because PHEMA exhibited a dithiocarbamate (DC) group at its terminal end. This system could be applied to the architecture of amphiphilic block copolymers. It was concluded that these polymerization systems proceeded with controlled radical mechanism. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 76–82, 2004     

Synthesis and characterization of magnetic and non-magnetic core-shell polyepoxide micrometer-sized particles of narrow size distribution

Core polystyrene microspheres of narrow size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2-methoxy ethanol. Uniform polyglycidyl methacrylate/polystyrene core-shell micrometer-sized particles were prepared by emulsion polymerization at 73 degrees C of glycidyl methacrylate in the presence of the core polystyrene microspheres. Core-shell particles with different properties (size, surface morphology and composition) have been prepared by changing various parameters belonging to the above seeded emulsion polymerization process, e.g., volumes of the monomer glycidyl methacrylate and the crosslinker monomer ethylene glycol dimethacrylate. Magnetic Fe(3)O(4)/polyglycidyl methacrylate/polystyrene micrometer-sized particles were prepared by coating the former core-shell particles with magnetite nanoparticles via a nucleation and growth mechanism. Characterization of the various particles has been accomplished by routine methods such as light microscopy, SEM, FTIR, BET and magnetic measurements.     

Synthesis and characterization of amphiphilic triblock copolymers by iron‐mediated atom transfer radical polymerization

The atom transfer radical polymerization of methyl methacrylate (MMA) and n‐butyl methacrylate (n‐BMA) was initiated by a poly(ethylene oxide) chloro telechelic macroinitiator synthesized by esterification of poly(ethylene oxide) (PEO) with 2‐chloro propionyl chloride. The polymerization, carried out in bulk at 90 °C and catalyzed by iron(II) chloride tetrahydrate in the presence of triphenylphosphine ligand (FeCl₂ · 4H₂O/PPh₃), led to A–B–A amphiphilic triblock copolymers with MMA or n‐BMA as the A block and PEO as the B block. A kinetic study showed that the polymerization was first‐order with respect to the monomer concentration. Moreover, the experimental molecular weights of the block copolymers increased linearly with the monomer conversion, and the molecular weight distribution was acceptably narrow at the end of the reaction. These block copolymers turned out to be water‐soluble through the adjustment of the content of PEO blocks (PEO content >90% by mass). When the PEO content was small [monomer/macroinitiator molar ratio (M/I) = 300], the block copolymers were water‐insoluble and showed only one glass‐transition temperature. With an increase in the concentration of PEO (M/I = 100 or 50) in the copolymer, two glass transitions were detected, indicating phase separation. The macroinitiator and the corresponding triblock copolymers were characterized with Fourier transform infrared, proton nuclear magnetic resonance, size exclusion chromatography analysis, dynamic mechanical analysis, and differential scanning calorimetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5049–5061, 2005     

Synthesis and miscibility studies of [60]fullerenated poly(2‐hydroxyethyl methacrylate)

[60]Fullerenated poly(2‐hydroxyethyl methacrylate)s containing 0.6–3.0 wt % C₆₀ were synthesized. These polymers are soluble in methanol and N,N‐dimethylformamide (DMF). [60]Fullerenated poly(2‐hydroxyethyl methacrylate)s with higher C₆₀ contents are only sparingly soluble in DMF and virtually insoluble in other organic solvents. A loading of 1.2 wt % C₆₀ in poly(2‐hydroxyethyl methacrylate) does not greatly affect its miscibility with poly(N‐vinyl‐2‐pyrrolidone), poly(1‐vinylimidazole), and poly(4‐vinylpyridine). © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 1157–1166, 2002     

Role of adsorbed chain rigidity in reinforcement of polymer nanocomposites

The thermomechanical behavior of polymer nanocomposites is mostly governed by interfacial properties which rely on particle–polymer interactions, particle loading, and dispersion state. We recently showed that poly(methyl methacrylate) (PMMA) adsorbed nanoparticles in poly(ethylene oxide) (PEO) matrices displayed an unusual thermal stiffening response. The molecular origin of this unique stiffening behavior resulted from the enhanced PEO mobility within glassy PMMA chains adsorbed on nanoparticles. In addition, dynamic asymmetry and chemical heterogeneities existing in the interfacial layers around particles were shown to improve the reinforcement of composites as a result of good interchain mixing. Here, the role of chain rigidity in this interfacially controlled reinforcement in PEO composites is investigated. We show that particles adsorbed with less rigid polymers improve the mechanical properties of composites. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 9–14     

Synthesis and characterization of well‐defined poly(2‐hydroxyethyl methacrylate‐co‐styrene)‐graft‐poly(ε‐caprolactone) by sequential controlled polymerization

A new graft copolymer, poly(2‐hydroxyethyl methacrylate‐co‐styrene) ‐graft‐poly(?‐caprolactone), was prepared by combination of reversible addition‐fragmentation chain transfer polymerization (RAFT) with coordination‐insertion ring‐opening polymerization (ROP). The copolymerization of styrene (St) and 2‐hydroxyethyl methacrylate (HEMA) was carried out at 60 °C in the presence of 2‐phenylprop‐2‐yl dithiobenzoate (PPDTB) using AIBN as initiator. The molecular weight of poly (2‐hydroxyethyl methacrylate‐co‐styrene) [poly(HEMA‐co‐St)] increased with the monomer conversion, and the molecular weight distribution was in the range of 1.09 ～ 1.39. The ring‐opening polymerization (ROP) of ?‐caprolactone was then initiated by the hydroxyl groups of the poly(HEMA‐co‐St) precursors in the presence of stannous octoate (Sn(Oct)₂). GPC and ¹H‐NMR data demonstrated the polymerization courses are under control, and nearly all hydroxyl groups took part in the initiation. The efficiency of grafting was very high. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 5523–5529, 2004