Methyl Methacrylate-divinylbenzene Research Articles

Innovative multifunctional nanocapsules with antibacterial, perfume, and UV-initiated coating properties

Polymer nanocapsules containing fragrance were fabricated for antibacterial, pleasing scent and UV-coating applications. Poly (2-methacryloyloxy dodecyl dimethyl ammonium chloride-4-allyloxy-2-hydroxybenzophenone)-block-polymethyl methacrylate-iodide (P(QAC12-BP)-b-PMMA-I) was first synthesized by solution iodine transfer polymerization (solution ITP) for use as a polymerizable surfactant in miniemulsion polymerization where benzalkonium chloride (BKC) was used as a cosurfactant. The nanocapsules were prepared using poly(methyl methacrylate–divinylbenzene) (P(MMA–DVB)) as a shell, whereas mangosteen oil (MO) was used as a fragrance core model for aroma. High colloidal stability nanocapsules with a size of about 213 nm were obtained. The nanocapsule surface contained QAC12 segments of 15.10 µmol/g-capsule (UV measurement), giving the high positive charge (+70 mV). An essential oil encapsulated inside the nanocapsule had a high encapsulation efficiency (>90%). The nanocapsules effectively inhibited bacterial growth because of QAC12 and BKC on their surface. The nanocapsules are able to coat the substrate via UV-activated covalent bonds of the BP segment.

Fabrication of porous polymer particles containing BiVO4 and Fe3O4 nanoparticles using block copolymer as porogen for effective dye removal

Hybrid porous particles (HPPs) of poly(methyl methacrylate-divinylbenzene) P(MMA-DVB) containing a visible light-photocatalyst bismuth vanadate (BiVO4) and magnetite (Fe3O4) nanoparticles (NPs) were synthesized and employed as a reusable material for effective dye removal. The porous structure increasing the surface to volume ratio and high water diffusivity of HPPs, prepared via the microsuspension iodine transfer polymerization, was generated by using poly(methacrylic acid)-block-poly(MMA-3-[trimethoxysilyl] propyl methacrylate) (PMAA-b-P(MMA-MPS)) as porogen. The block copolymer also acting as a surface modifier of BiVO4 NPs allowed the encapsulation of this photocatalyst together with oleic acid coated Fe3O4 NPs in spherical HPPs. The fabricated HPPs could efficiently remove methylene blue (MB) up to 235 mg/g-BiVO4 based on the adsorption and photocatalytic degradation mechanism caused by the particle porosity and BiVO4 NPs, respectively. Moreover, the incorporated Fe3O4 NPs provided the magnetic separation ability of the HPPs for their reusability up to 5 cycles with a high MB removal performance of > 86. These HPPs would be good candidates for effective dye removal in contaminated water

Removal of naphthalene from aqueous systems by poly(divinylbenzene) and poly(methyl methacrylate-divinylbenzene) resins

Treatment of the oily wastewater from crude oil extraction is a growing challenge due to rising concern for the environment. Polyaromatic hydrocarbons (PAHs) deserve special attention because of their high toxicity. There is a need to develop processes able to minimize the discharge of these compounds and analytic techniques to monitor the levels of PAHs in aqueous media. In this study poly(methyl methacrylate-divinylbenzene) (MMA-DVB) and poly(divinylbenzene) (DVB) were assessed with respect to their capacity to retain naphthalene (NAF) in continuous flow and batch processes (adsorption equilibrium and kinetics). The analytic techniques applied were gas chromatography and spectrofluorimetry, which was adapted for quantification of NAF. The batch adsorption studies showed that DVB is more efficient in adsorption than MMA-DVB, and the Freundlich model and pseudo-second-order model better fitted the equilibrium data and adsorption kinetics, respectively. The elution results showed that both resins are highly efficient in removing NAF, with DVB outperforming MMA-DVB. However, MMA is cheaper raw material, making MMA-DVB more competitive for treatment of oily wastewater. The resins were regenerated by eluting about 7.2 and 2.5 L of methanol:water (70:30 v/v), respectively for DVB and MMA-DVB. Regarding to the useful life after regeneration, the resins presented a reduction about 30%, relating to zero concentration of NAF.

Síntese e sulfonação de resinas poliméricas macroporosas e avaliação na remoção de petróleo e de anilina em água

Polymeric resins have been widely used in water treatment processes due to their advantages, such as high selectivity and possibility of regeneration and chemical modification, allowing obtaining a material with greater selectivity/specificity. In the present study, porous polymeric resins of methyl methacrylate-divinylbenzene (MMA-DVB), styrene-divinylbenzene (Sty-DVB) and sulfonated styrene-divinylbenzene (S-Sty-DVB) were synthesized, characterized and evaluated for their efficiency in removing oil and aniline contained in water. In the tests with oily water, the efficiency in removing oil and cations of sodium and calcium was assessed with columns containing only one type of resin (Sty-DVB or S-Sty-DVB) and columns containing blended filling (MMA-DVB/S-Sty-DVB and Sty-DVB/S-Sty-DVB). The columns containing the mixture performed better, due to the diverse hydrophilicity of the adsorbent system, allowing removal of a wider range of contaminants. The removal of aniline from the water was possible with the use of the sulfonated styrene-divinylbenzene because of the reaction between the aniline and acidic sites of the resin. The efficiency of this resin in removing aniline declined gradually rather than abruptly, due to the interaction of the aniline molecules with the aniline salt formed after saturation of the resin's acidic sites.

Preparation of macroporous polyHIPE foams via radiation-induced polymerization at room temperature

PolyHIPEs are highly porous, crosslinked polymer foams typically synthesized within high internal-phase emulsions (HIPEs). Two kinds of polyHIPEs including poly(styrene-divinylbenzene) [P(St-DVB)] and poly(methyl methacrylate-divinylbenzene) [P(MMA-DVB)] foams are synthesized in this work, which are fabricated from HIPEs template via radiation-induced polymerization at room temperature. Traditional free radical polymerization initiated by potassium peroxydisulfate (KPS) at 60 °C for producing polyHIPE P(St-DVB) foams is also conducted for comparison. It is found that the amount of emulsifier can be reduced greatly in the radiation-induced polymerization of HIPEs at room temperature, compared with the traditional polymerization approach. Besides, P(MMA-DVB) PolyHIPE foams with a fine microstructure of highly interconnected pores have been successfully fabricated via radiation-induced polymerization in this work, which is usually difficult to be prepared by thermal-initiation method because of the intermediate hydrophobicity of methyl methacrylate monomer. The influences of the fraction of internal aqueous phase and the concentration of emulsifier on the structure and performance of foams are carefully explored. The structure and compression strength of the foams are characterized by scanning electron microscopy and a mechanical testing machine, respectively.

Synthesis and simple method of estimating macroporosity of methyl methacrylate–divinylbenzene copolymer beads

AbstractMacroporous methyl methacrylate–divinylbenzene copolymer beads having diameter ∼ 300 μm were synthesized by free radical suspension copolymerization. The macroporosity was generated by diluting the monomers with inert organic liquid diluents. The macroporosity was varied in the range of ∼0.1 to ∼ 1.0 mL/g by varying a number of porosity controlling factors, such as the diluents, solvent to nonsolvent mixing ratios when employing a mixture of the two diluents, degree of dilution, and crosslinkage. Increase in pore volume from 0.1 to 0.45 mL/g resulted in a sharp increase in mesopores having diameters in the range of 3–20 nm whereas the macropores remained negligible when compared with mesopores. Increase in pore volume from 0.45 to 1 mL/g resulted in a sharp increase in macropores, whereas mesopores having diameters in the range of 3–20 nm remained almost constant. The mesopores having diameters in the range of 20–50 nm showed an increase with the increase in pore volume throughout the whole range of pore volume studied. Macroporosity characteristics, i.e., pore volume (Vm), surface area (SA), and pore size distributions were evaluated by mercury penetration method. Statistical analysis of the data obtained in the present study shows that the macroporosity characteristics can be estimated with a reasonable accuracy from the pore volumes, which in turn are determined from the densities of the copolymers. These results are explained on the basis of pore formation mechanism. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008

Preparation of magnetic poly(methylmethacrylate–divinylbenzene–glycidylmethacrylate) microspheres by spraying suspension polymerization and their use for protein adsorption

Moderately uniform magnetic poly(methylmethacrylate–divinylbenzene–glycidylmethacrylate) microspheres (poly(MMA–DVB–GMA) microspheres) were prepared by spraying suspension copolymerization of methyl methacrylate, divinylbenzene and glycidyl methacrylate in the presence of Fe 3O 4 magnetic fluid. A protein adsorption assay indicated that these magnetic microspheres could significantly improve the capacity of protein adsorption.

Fe2+ and Fe3+ adsorption on 2‐vinylpyridine–divinylbenzene copolymers and acrylonitrile–methyl methacrylate–divinylbenzene terpolymers

AbstractThe adsorption of Fe2+ and Fe3+ ions on 2‐vinylpyridine–divinylbenzene copolymer and acrylonitrile–methyl methacrylate–divinylbenzene terpolymer was investigated. In general, the adsorption of Fe2+ and Fe3+ in both resins increased with the enhancement of hydrochloric acid and metal concentration. The metal adsorption on the terpolymer increased sharply with the addition of small portions of ethanol, whereas the adsorption on the copolymer practically was not affected by the presence of the alcohol. An increase in temperature produced a small increase in iron adsorption for both resins. Fourier transform infrared spectra showed that nitrile and ester groups of the terpolymer did not suffer hydrolysis during metal adsorption, even for the highest HCl concentration and the highest temperature applied. A mechanism of iron adsorption through the ion exchange of chloride anions by tetrahedral [FeCl4]2− or [FeCl4]− anions is proposed. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3905–3912, 2003

Metalization of polymer beads via polymer-supported hydrazines as reducing agents

A new method for depositing metal onto a polymer surface has been developed in which the metal coating of polymer beads is performed with hydrazine functions as reducing agents on the surface of the polymer itself. In this study, glycidyl methacrylate–methyl methacrylate–divinyl benzene terpolymer was prepared as spherical beads with a suspension polymerization methodology. Beads of the polymer sample (210–420-μm fraction) containing 3.4 mmol g−1 epoxy were treated with an excess of hydrazinium hydroxide to yield a polymer with 2.3 mmol g−1 hydrazine functions. The hydrazine functions on the polymer surfaces were efficient in metal reductions. Therefore, the modified bead polymer samples, when soaked in aqueous ammonia solutions of Ni(II), Ag(I), and Cu(II) ions (0.1 M), were covered rapidly by the corresponding zero-valent metal ions. Metal deposition took place almost quantitatively (ca. 4.5 mmol/g of the polymer) within 60 min of the contact times. The accumulations of metal were followed visually and occurred only on the polymer beads. There was no evidence that the reaction occurred within the solution. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 748–754, 2002; DOI 10.1002/pola.10158

Antibacterial activity of resin-containing triethylenetetramine side chains and/or thiol groups-metal complexes

Four chelating resins containing triethylenetetramine side chains and/or thiol groups were made from macroreticular 2,3-epithiopropyl methacrylate, styrene–divinylbenzene (DVB), or methyl methacrylate–DVB copolymer beads, and then the resins bearing metal ions such as Ag+, Cu2+, and Zn2+ were made. The antibacterial activity of the resins bearing metal ions against Escherichia coli (E. coli) or Staphylococcus aureus (S. aureus) was investigated. The resins containing thiol groups showed the higher adsorption capacity for silver ions than for other metal ions. The resins, which contain both triethylenetetramine side chains and thiol groups, bearing silver ions (RE-TTA-Ag) exhibited high antibacterial activity against bacteria, especially E. coli, without the residual silver ions in water after contacting with bacteria. The activity of the RE-TTA-Ag did not decrease even after reusing several time. © 1996 John Wiley & Sons, Inc.

Formation mechanism of silicone rubber particles with core-shell structure by seeded emulsion polymerization

Silicone rubber particles with core–shell structure were prepared by polymerization of vinyl monomers in the presence of crosslinked and linear poly(dimethyl siloxane-methyl vinyl siloxane) latex. The monomers were added with either continuous or swelled-continuous addition mode. The core–shell morphology of silicone rubber/polystyrene [PST] and silicone rubber/poly(methyl methacrylate-divinyl benzene) [P(MMA-DVB)] composite particles were obtained. The effects of monomer addition mode, the compatibilities of the monomers or their homopolymer with silicone rubber, and the reactivity of polysiloxane with vinyl monomers on the formation of the core–shell structure were discussed. © 1996 John Wiley & Sons, Inc.

Copolymerization of glycidylmethacrylate–methylmethacrylate–divinylbenzene in cyclohexane

The copolymerization of glycidylmethacrylate–methylmethacrylate–divinylbenzene in cyclohexane was studied as an example of crosslinking precipitation copolymerization. The resultant copolymer is fine spheroidal. The copolymerization proceeds acceleratively at first, then steadily, and gradually slows down. The larger the divinylbenzene concentration, the smaller is the copolymerization rate. Glycidylmethacrylate is preferentially incorporated in the copolymer.

Preparation of Macroreticular Chelating Resins Containing Hydrazide. Groups and Adsorption of Metal Ions on Them

The preparation of the macroreticular chelating resins containing 'hydrazide groups by the hydrazinolysis of macroreticular methyl methacrylate-divinylbenzene copolymer with h ydrazine hydrate was carried out and adsorption of metal ions on these resins was tested.It was found that the hydrazinolysis of these copolymers was accompanied by the formation of carboxyl groups in an early stage of the reaction and the carboxyl groups thus formed converted into hydrazide groups during a subsequent reaction at a high temperature. The good chelating resins were prepared by the hydrazinolysis of macroreticular copolymer for 5 9 hours at 175°C. This copolymer was obtained with the following compositions: methyl methacrylate 90-95% (volume), divinylbenzene 5-10% (volume) and isooctane 50% (volume) per the monomer. As the chelating resins had a few carboxyl groups, the adsorption of CA2+ occurred at higher pH values than 4. But the chelating resins exhibited selectivity for certain metal ions, which was liable to form ammine complexes, and showed a special high affinity toward Hg2+ or Cu2+ at lower pH values than 4. The separation of the certain metal ions could easily be carried out by varying the pH; the adsorption of these metal ions was scarcely influenced by other ion, e. g., K+ or Na+.

Preparation of Chelating Resins from Methyl Methacrylate-Divinylbenzene Copolymer and Absorptivity of Metal lons

The preparation of the chelating resins containing polyamino greups by the aminolysis of methyl methacrylate-divinylbenzen e copoly er with polyethylene polya ine and its absorptivity of metal ions were investigated.The aminolysis of these copolymers was comparatively easy run and it was found that the aminolysis was accompanied by the introduction of carbexyl groups in an early stage of the reaction and the earboxyl greups thus formed were converted into amide groups in a subsequent reaction at high temperaturesFor the aminelysis to prepare the favorabSe chelating resins, triethylene tetramine or tetraethylene pentamine was suitable.The good chelating resins were prepared by the aminolysis (170N1800C; 5. vlO hr) of macroreticular copolymer which was obtained under the following conditions: isoectane ratie was 50% (volume) per the monomer consisting of methyl methacrylate 92 v95%e (volume) and divinylbenzene 5, v8%e (volume).These ehelating resins had a few carboxyl groups but did net shew the absorptivity of Caa for pH values less than 9 and the separation of the definite metal ien from the the solution, containing the certain metal ions which exhibited a tendency to form ammine complex, could be carried out by adjusting its pH values.