Synthesis and characterization of poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) copolymer beads for heavy‐metal removal

We prepared poly(ethylene glycol dimethacrylate–1‐vinyl‐1,2,4‐triazole) [poly(EGDMA–VTAZ)] beads (average diameter = 150–200 μm) by copolymerizing ethylene glycol dimethacrylate (EGDMA) with 1‐vinyl‐1,2,4‐triazole (VTAZ). The copolymer composition was characterized by elemental analysis and found to contain five EGDMA monomer units for each VTAZ monomer unit. The poly(EGDMA–VTAZ) beads had a specific surface area of 65.8 m²/g. Poly(EGDMA–VTAZ) beads were characterized by Fourier transform infrared spectroscopy, elemental analysis, surface area measurements, swelling studies, and scanning electron microscopy. Poly(EGDMA–VTAZ) beads with a swelling ratio of 84% were used for the heavy‐metal removal studies. The adsorption capacities of the beads for Cd(II), Hg(II), and Pb(II) were investigated in aqueous media containing different amounts of these ions (5–750 mg/L) and at different pH values (3.0–7.0). The maximum adsorption capacities of the poly(EGDMA–VTAZ) beads were 85.7 mg/g (0.76 mmol/g) for Cd(II), 134.9 mg/g (0.65 mmol/g) for Pb(II), and 186.5 mg/g (0.93 mmol/g) for Hg(II). The affinity order toward triazole groups on a molar basis was observed as follows: Hg(II) > Cd(II) > Pb(II). pH significantly affected the adsorption capacity of the VTAZ‐incorporated beads. The equilibrium data were well fitted to the Redlich–Peterson isotherm. Consideration of the kinetic data suggested that chemisorption processes could have been the rate‐limiting step in the adsorption process. Regeneration of the chelating‐beads was easily performed with 0.1M HNO₃. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4276–4283, 2006     

A Rapid and Efficient Synthesis of Quinone Derivatives: Ru(II)‐ or Ir(I)‐Catalyzed Hydrogen Peroxide Oxidation of Phenols and Methoxyarenes

Hydroquinone and methoxybenzene derivatives were catalytically oxidized promptly to the corresponding quinones in up to 99% yield. With a catalyst loading of 0.01 mol %, a maximum TON of 8.4×10³ was attained in the case of Ru(II)‐complex. Ru(II)(pybox‐dh)(pydic) is able to enhance the hydrogen peroxide oxidation of substituted hydroquinones as well as methoxybenzenes, but Ir[(coe)₂Cl]₂ and Ir[(cod)Cl]₂ were found to be effective catalysts only for the former substrates under similar oxidation conditions.     

Preparation and swelling properties of solution crosslinked poly(cis‐1,4‐butadiene) gels

Poly(cis‐1,4‐butadiene) (PCB) gels were prepared by the crosslinking polymerization of 4‐tert‐butylstyrene (tBS) and divinylbenzene (DVB) onto unvulcanized butadiene rubber with a solution polymerization technique with benzoyl peroxide (BPO) as an initiator. The effects of the reaction conditions, such as the amount of the solvent, the amount of DVB and tBS, and the initiator (BPO), on the equilibrium swelling ratio (Q_e) were also investigated. The highest oil absorbencies of crosslinked gels in xylene and cyclohexane were 51.35 and 32.98 g/g, respectively. A swelling kinetic equation was proposed for this system: Q_t = Q_e ? {Kt + [1/(Q_e ? Q₀)]}^?1, where Q_t is the swelling ratio at time t, Q₀ is the initial swelling ratio, and K is the swelling kinetic constant. This equation fit the experimental results quite well. The diffusion of organic solvents in PCB gels was Fickian. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 2241–2245, 2003     

Advanced oxidation processes for the degradation of p‐hydroxybenzoic acid 2: Photo‐assisted Fenton oxidation

Oxidation of p‐hydroxybenzoic acid in aqueous solution by the photo‐assisted Fenton reaction (Fe²⁺ + H₂O₂ + UV) has been studied. The effects of ferrous ion concentration (0.05, 0.14 and 0.29 mmol dm^?3), temperature (10, 20, 30 and 40 °C), and initial hydrogen peroxide concentration (0.7, 1.4, 2.2 and 2.9 mmol dm^?3) on the p‐hydroxybenzoic acid conversion were established. Experimental results indicate that the kinetics of this oxidation process fits pseudo‐first‐order kinetics well. The overall kinetic rate constant was split into two components: direct oxidation by UV radiation (photolysis) and oxidation by free radicals (mainly OH·) generated in the system. The importance of these two reaction paths for each specific value of ferrous ion concentration, temperature and initial hydrogen peroxide concentration was evaluated. A semi‐empirical expression is proposed for the overall reaction rate which takes into account both oxidation pathways and is a function of operating variables. © 2001 Society of Chemical Industry     

Syntheses and characterization of polystyrene‐supported 2,5‐dimercapto‐1,3,4‐thiodiazole and its sorption behavior for Pd(II), Pt(IV), and Au(III)

A type of chelating resin crosslinking polystyrene‐supported 2,5‐dimercapto‐1,3,4‐thiodiazole (also called bismuththiol I, BMT), containing sulfur and nitrogen atoms, was prepared. The structure of PS‐BMT was confirmed by FTIR, elemental analysis, and X‐ray photoelectron spectroscopy (XPS). Adsorption of Pd(II), Pt(IV), and Au(III) was investigated. The capacity of PS‐BMT to adsorb Pd(II) and Pt(IV) was 0.190 and 0.033 mmol/g, respectively. The adsorption dynamics of Pd(II) showed that adsorption was controlled by liquid film diffusion and that the apparent activation energy, E_a, was 32.67 kJ/mol. The Langmuir model was better than the Freundlich model in describing the isothermal process of Pd(II), and the ΔG, ΔH, and ΔS values calculated were ?0.33 kJ/mol, 26.29 kJ/mol, and 87.95 J mol^?1 K^?1, respectively. The mechanisms of adsorption of Pd(II), Pt(IV), and Au(III) were confirmed by XPS. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 631–637, 2006     

Characterization of macroporous 1‐vinyl‐2‐pyrrolidone copolymers obtained by suspension polymerization

Radical suspension copolymerization of 1‐vinyl‐2‐pyrrolidone (VP) with three different cross‐linkers: divinylbenzene (DVB), trimethylolpropane trimethacrylate (TRIM), and di(methacryloxymethyl) naphthalene (DMN) was used to prepare macroporous microspheres. During the copolymerization, the mixture of toluene and n‐dodecane as a pore‐forming diluent was used. All samples were characterized in terms of particle size and distribution, nitrogen content, specific surface area total pore volume, and pore size distribution. It was found that specific surface area of the obtained beads is strongly dependent on the diluent system and the type of cross‐linker and achieves value from 27 to 845 m²/g. To determine the influence of chemical structure of cross‐linkers on the selectivity and polarity of the copolymers, inverse gas chromatography was applied. In addition, VP–DVB and VP–DMN copolymers were modified by sulfonation into cation‐exchangers with cation exchange capacity equal 1.98 and 2.31 mmol/g, respectively. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Monodisperse‐porous N‐methyl‐D‐glucamine functionalized poly(vinylbenzyl chloride‐co‐divinylbenzene) beads as boron selective sorbent

To generate a new sorbent with high boron adsorption capacity, we synthesized monodisperse‐porous poly(vinylbenzyl chloride‐co‐divinylbenzene), poly(VBC‐co‐DVB), beads 8.5 μm in size by a new “modified seeded polymerization” technique. By using their chloromethyl functionality, the beads were derivatized by a simple, direct reaction with a boron‐selective ligand, N‐methyl‐D ‐glucamine (NMDG). The selection of poly(VBC‐co‐DVB) beads as a starting material allowed to obtain high boron sensitive‐ligand density on the beads depending on their high chloromethyl content. In the batch adsorption runs performed using NMDG‐attached poly(VBC‐co‐DVB) beads as sorbent, boron removal was efficiently performed in a wide pH range between 4 and 11. Quantitative boron removal was observed with the sorbent concentration of 4 g/L. In the same runs, plateau value of equilibrium adsorption isotherm was obtained as 14 mg boron/g beads. Relatively higher boron adsorption was explained by high ligand density and high specific surface area of the sorbent. Boron adsorption isotherms were analyzed using Langmuir and Freundlich models. In the kinetic runs performed for boron removal, the equilibrium was attained within 10 min at a value of 98%. The fast kinetic behavior was explained by the smaller particle size and enhanced porosity of the new sorbent. Infinite solution volume model and unreacted core model were used to evaluate boron adsorption onto the NMDG‐attached poly(VBC‐co‐DVB) beads. The results indicated that the adsorption process is controlled by the particle‐diffusion step. © 2012 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Segregation of resin‐bound peptides during solid‐phase synthesis

To compare the segregation ability of 1,4‐butanediol dimethacrylate‐crosslinked polystyrene (BDDMA‐PS) and divinylbenzene‐crosslinked polystyrene (DVB‐PS), a set of difficult sequence peptides characterized by high‐arithmetic‐average β‐sheet stabilizing potential (SP_β) and low‐stepwise arithmetic average random coil conformational parameter (P_c*) were synthesized on both supports (～ 2 mmol Cl g^?1) under identical conditions. The yield and purity of the peptides obtained from BDDMS‐PS resin were higher than from DVB‐PS resin. The synthetic efficiency of the new support was found to be its ability to suppress the aggregation of growing peptide chains by β‐sheet formation. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1717–1723, 2002     

Fe(PyTACN)‐Catalyzed cis‐Dihydroxylation of Olefins with Hydrogen Peroxide

A family of iron complexes with general formula [Fe(II)(^R,Y,XPyTACN)(CF₃SO₃)₂], where ^R,Y,XPyTACN=1‐[2′‐(4‐Y‐6‐X‐pyridyl)methyl]‐4,7‐dialkyl‐1,4,7‐triazacyclononane, X and Y refer to the groups at positions 4 and 6 of the pyridine, respectively, and R refers to the alkyl substitution at N‐4 and N‐7 of the triazacyclononane ring, are shown to be catalysts for efficient and selective alkene oxidation (epoxidation and cis‐dihydroxylation) employing hydrogen peroxide as oxidant. Complex [Fe(II)(^Me,Me,HPyTACN)(CF₃SO₃)₂] ( 7 ), was identified as the most efficient and selective cis‐dihydroxylation catalyst among the family. The high activity of 7 allows the oxidation of alkenes to proceed rapidly (30 min) at room temperature and under conditions where the olefin is not used in large amounts but instead is the limiting reagent. In the presence of 3 mol% of 7 , 2 equiv. of H₂O₂ as oxidant and 15 equiv. of water, in acetonitrile solution, alkenes are cis‐dihydroxylated reaching yields that might be interesting for synthetic purposes. Competition experiments show that 7 exhibits preferential selectivity towards the oxidation of cis olefins over the trans analogues, and also affords better yields and high [syn‐diol]/[epoxide] ratios when cis olefins are oxidized. For aliphatic substrates, reaction yields attained with the present system compare favourably with state of the art Fe‐catalyzed cis‐dihydroxylation systems, and it can be regarded as an attractive complement to the iron and manganese systems described recently and which show optimum activity against electron‐deficient and aromatic olefins.     

Studies on two‐dimensional coordination polymer cadmium phosphate and its high efficient adsorption of Pb(II) ions from aqueous solutions

The two‐dimensional coordination polymer cadmium phosphate with the morphology of rectangle layers was prepared by solid‐state template reaction at room temperature, and was characterized by XRD, FTIR, and TEM techniques. The as‐synthesized sample is a layered cadmium phosphate material, in which the structure is poly (CdPO₄^?) anion framework with ammonium ions and water species residing in the space between the layers, and cadmium ions are coordinated by the phosphate oxygen atoms. This article also presents the adsorption of Pb(II) ions from aqueous solution on the as‐synthesized coordination polymer cadmium phosphate, and the results showed that this inorganic polymer adsorbent had good adsorption capacity. It could reach to the saturation adsorption capacity within an hour, and its excellent adsorption capacity for Pb(II) was 5.50 mmol/g when the initial solution concentration was 1.68 × 10³ μg/mL at T = 278K. Moreover, the adsorption kinetics and adsorption isotherms were studied, it revealed that the adsorption kinetics can be modeled by pseudo second‐order rate equation wonderfully. The apparent activation energy (E_a), ΔG, ΔH, and ΔS were 3.16 kJ mol^?1, ?13.97 kJ mol^?1, ?11.84 kJ mol^?1, and 7.66 J mol^?1 K^?1, respectively. And it was found that Langmuir equation could well interpret the adsorption of the as‐synthesized coordination polymer cadmium phosphate for Pb(II) ions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Preparation,characterization, and metal ion retention capacity of Co(II) and Ni(II) from poly(p‐HO‐ and p‐Cl‐phenylmaleimide‐co‐2‐hydroxypropylmethacrylate) using the ultra filtration technique

p‐Chlorophenylmaleimide and p‐hydroxyphenylmaleimide with 2‐hydroxypropyl methacrylate were synthesized by radical polymerization, and the metal ion retention capacity and thermal behavior of the copolymers were evaluated. The copolymers were obtained by solution radical polymerization with a 0.50 : 0.50 feed monomer ratio. The maximum retention capacity (MRC) for the removal of two metal ions, Co(II) and Ni(II) in aqueous phase were determined using the liquid‐phase polymer based retention technique. Inorganic ion interactions with the hydrophilic polymer were determined as a function of pH. The metal ion retention capacity does not depend strongly on the pH. Metal ion retention increased with an increase of pH for a copolymer composition 0.50 : 0.50. At different pH, the MRC of the poly(p‐chlorophenylmaleimide‐co‐2‐hydroxypropylmethacrylate) for Co(II) and Ni(II) ions varied from 44.1 to 48.6 mg/g and from 41.5 mg/g to 46.0 mg/g, respectively; while the MRC of poly(p‐hydroxyphenylmaleimide‐co‐2‐hydroxypropyl methacrylate) for Co(II) and Ni(II) ions varied from 28.4 to 35.6 mg/g and from 27.2 to 30.8 mg/g, respectively. The copolymers and copolymer–metal complexes were characterized by elemental analysis, FT‐IR, ¹H NMR spectroscopy, and thermal behavior. The thermal behavior of the copolymer and polymer–metal complexes were studied using differential scanning calorimetry and thermogravimetry techniques under nitrogen atmosphere. The thermal decomposition temperature and T_g were influenced by the binding‐metal ion on the copolymer. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Degradation of benzene,toluene ethylbenzene and p‐xylene (BTEX) in aqueous solutions using UV/H2O2 system

The homogeneous degradation of benzene (B), toluene (T), ethylbenzene (E) and p‐xylene (X) (BTEX) was studied in aqueous solutions, at pH 3.0, of hydrogen peroxide (5.8 mM ) under UV irradiation in a photoreactor equipped with a 300 nm lamp of light intensity 3.5 × 10^?5 Ein L^?1 min^?1. BTEX was substantially degraded by the H₂O₂/UV system, with >90% disappearing in 10 min of irradiation. The decomposition of BTEX was studied either as single or as multi‐component systems. The effects of irradiation time, amounts of H₂O₂ in molar ratios, rate of degradation and competition between components were thoroughly examined. It can be stated that the rate of BTEX degradation in mixture was higher than those for the individual components due to external effects of the absorption of UV light by the mixture, and their effects on enhancing the formation of OH^? radicals. The appropriate figure of merit, the electrical energy per mass (EE/M), was estimated at various molar ratios and it was confirmed that the best value was the one depicted for p‐xylene (0.065 kWh kg^?1). A theoretical model for the degradation pathway was proposed. Copyright © 2004 Society of Chemical Industry     

Preparation and Characterization of the Newly Synthesized Metal‐Complexing‐Ligand N‐Methacryloylhistidine Having PHEMA Beads for Heavy Metal Removal from Aqueous Solutions

The aim of this study was to investigate in detail the performance for removal of heavy metal ions of beads composed of poly(2‐hydroxyethyl methacrylate) (pHEMA) to which N‐methacryloylhistidine (MAH) was copolymerized. The metal‐complexing ligand MAH was synthesized by using methacryloyl chloride and histidine. Spherical beads with an average size of 150–200 μm were obtained by the radical suspension polymerization of MAH and HEMA conducted in an aqueous dispersion medium. Owing to the reasonably rough character of the bead surface, p(HEMA‐MAH) beads had a specific surface area of 17.6 m²/g. The synthesized MAH monomer was characterized by NMR; p(HEMA‐MAH) beads were characterized by swelling studies, FTIR and elemental analysis. The p(HEMA‐MAH) beads with a swelling ratio of 65%, and containing 1.6 mmol MAH/g, were used in the adsorption/desorption experiments. Adsorption capacity of the beads for the selected metal ions, i. e., Cu(II), Cd(II), Cr(III), Hg(II) and Pb(II), were investigated in aqueous media containing different amounts of these ions (10–750 mg/L) and at different pH values (3.0–7.0). Adsorption equilibria were established in about 20 min. The maximum adsorption capacities of the p(HEMA‐MAH) beads were 122.7 mg/g for Cu(II), 468.8 mg/g for Cr(III), 639.4 mg/g for Cd(II), 714.1 mg/g for Pb(II) and 1 234.4 mg/g for Hg(II). pH significantly affected the adsorption capacity of MAH incorporated beads. The chelating beads can be easily regenerated by 0.1 M HNO₃ with high effectiveness. These features make p(HEMA‐MAH) beads a potential candidate for heavy metal removal at high capacity.     

Liquid–liquid extraction of cadmium(II) by Cyanex 923 and its application to a solid‐supported liquid membrane system

The extraction of cadmium(II) by Cyanex 923 (a mixture of alkylphosphine oxides) in Solvesso 100 from hydrochloric acid solution has been investigated. The extraction reaction is exothermic. The numerical analysis of metal distribution data suggests the formation of CdCl₂.2L, HCdCl₃.2L and H₂CdCl₄.2L (L = ligand) in the organic phase. The results obtained for cadmium(II) distribution have been implemented in a solid‐supported liquid membrane system. The influences of feed phase stirring speed (400–1400 min^?1), membrane composition (carrier concentration: 0.06–1 mol dm^?3) and metal concentration (0.01–0.08 g dm^?3) on cadmium transport have been investigated. Copyright © 2005 Society of Chemical Industry     

Sorption capacity of a new generation granular activated carbon—Bio‐Sep® bead—and its use in a suspended growth bioreactor

BACKGROUND: A new generation granular activated carbon—Bio‐Sep® beads—consist of 25% polymer (Nomex) and 75% powdered activated carbon. The porous structure and high surface area of these beads make them suitable for sorbent in adsorption columns, and for immobilization media in bioreactors. The aim of this study was to study the sorption characteristics of Bio‐Sep® beads for methyl t‐butyl ether (MTBE) and t‐butyl alcohol (TBA), and to demonstrate the advantage of their usage in a suspended growth bioreactor. RESULTS: The maximum uptake capacity of Bio‐Sep® beads for MTBE and TBA, in the studied concentration range (10–100 mg L^?1), was observed to be 9.73 and 6.23 mg g^?1, respectively. A 52 h desorption experiment resulted in 13.6–42.2% MTBE and 33–53% TBA desorption corresponding to the initial solid phase concentrations of 1.68–9.73 mg g^?1 and 1.41–6.23 mg g^?1, respectively. The sorption of TBA on the Bio‐Sep® beads was significantly hindered by the presence of MTBE. The addition of 10 g Bio‐Sep® beads (dry weight) in a suspended growth bioreactor was able to eliminate the inhibitory effect of 150 mg L^?1 MTBE. CONCLUSIONS: At an equilibrium aqueous phase concentration (C_e) of 1 mg L^?1, the solid phase concentration (q_e) on Bio‐Sep® beads were observed as 1.44 and 0.47 mg g^?1 for MTBE and TBA, respectively. The results obtained in this study indicate that Bio‐Sep® beads have reasonable sorption and desorption characteristics, which can be successfully exploited for the removal/degradation of toxic organic pollutants in high rate bioreactors. Copyright © 2007 Society of Chemical Industry     

Synthesis of zwitterionic stationary phase based on hydrophilic non‐porous poly(glycidymethacrylate‐co‐ethylenedimethacrylate) beads and their application for fast separation of proteins

A new hydrophilic strong/strong type zwitterionic stationary phase for high performance liquid chromatography (HPLC) was synthesized by chemical modification of 3.0 μm non‐porous monodisperse poly(glycidylmethacrylate‐co‐ethylenedimethacrylate)(P_GMA/EDMA) beads in the following steps. First, the beads were reacted with hydrochloride to obtain chlorizated beads; second, chlorizated beads were reacted with dimethylamine to obtain ammoniated beads; third, ammoniated beads were reacted with 1,3‐propanesultone to obtain non‐porous hydrophilic zwitterionic stationary phase. The stationary phase was evaluated in detail to determine its ion‐exchange properties, separability, reproducibility, hydrophilicity, and the effect of column loading and pH on the separation and retention of proteins. The highest dynamic protein loading capacity of the synthesized zwitterionic packing for bovin serum albumin and Lys were 18.3 and 27.4 mg g^?1, respectively. The zwitterionic stationary phase was capable of separating two acidic and three basic proteins simultaneously in less than 2.5 min by the flow‐rates of 3.0 mL min^?1. The zwitterionic resin was also used for rapid separation and purification of recombinant human interferon‐r (rhIFN‐r) and human granulocyte colony‐stimulation factor (hG‐CSF) from the crude extract solution. The satisfactory results were obtained. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of porous poly(sodium acrylate‐co‐acrylamide) salt‐resistant superabsorbent composite

A novel semi‐interpenetrating polymer networks (semi‐IPNs) porous salt‐resistant superabsorbent composite was prepared by copolymerization of partially neutralized acrylic acid and acrylamide using polyethylene glycol as semi‐IPNs composite, N,N′‐methylenebisacrylamide, triene propanol phosphate, and trihydroxymethyl propane glycidol ether as crosslinking agents, methanol, propanol, and butanol as foaming agents, and L ‐ascorbic acid and peroxide hydrogen as initiators. To improve the properties of swollen hydrogel, such as strength, resilience, permeabilities, and dispersion, the copolymer was surface‐crosslinked, and then blended with aluminum sulfate, sodium carbonate, and sodium 1‐octadecanol phosphate in the course of post treatment. The influences of reaction conditions on properties of superabsorbent composite were investigated and optimized, and the water absorbency of superabsorbent composite prepared at optimal conditions in 0.9 wt% NaCl aqueous solution under atmospheric pressure and certain load (P ≈ 2 × 10³ Pa) were 61 g g^?1 and 16.7 g g^?1, respectively. Moreover, the swelling rate reached 22.003 × 10^?3 g (g s)^?1. And the excellent hydrogel properties, such as hydrogel strength, resilience, permeabilities, and dispersion were also obtained. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Self‐assembled centimetre‐sized rods obtained in the oxidation of o‐phenylenediamine and aniline

Morphologically well‐defined rods of approximately 1 cm in length are effectively and economically obtained by mixing ortho‐phenylenediamine (30 mmol L^?1) with ammonium persulfate (12.5 mmol L^?1) in an acidic solution (0.37 mol L^?1 HCl) at room temperature with and without the presence of 50 mmol L^?1 aniline. These self‐assembled, morphologically uniform products can be potentially scaled up and used as morphological templates to fabricate well‐defined structures of other materials such as conducting polymers. The products were characterized using Raman, UV‐visible, high‐resolution NMR (¹H and ¹³C) and mass spectroscopies, X‐ray diffraction, scanning electron microscopy and elemental analysis. Apart from certain differences in visual appearance and in X‐ray diffractograms, other analytical data suggest that there are no structural changes upon addition of aniline into the reaction mixture. NMR and mass spectra imply that all syntheses carried out either with or without aniline result in a mixture of two products, attributed to 2,3‐phenazinediamine and 3‐aminophenazin‐2‐ol. A formation mechanism based on hydrogen bonding and π–π stacking has been proposed. © 2015 Society of Chemical Industry     

Poly(N‐isopropylacrylamide) gel‐based macroporous monolith for continuous‐flow recovery of palladium(II) ions

Macroporous monoliths, composed of thermoresponsive, tertiary‐aminated, and crosslinking monomers, were prepared for continuous‐flow separation of palladium(II) ions. N ‐Isopropylacrylamide was required to form the porous structure in the monoliths, indicating that the mechanism of porous structure formation involved polymerization‐induced phase separation of the poly(N ‐isopropylacrylamide) gel. Tertiary‐aminated monoliths showed adsorption selectivity for palladium(II) ions in hydrochloric media, compared with copper(II) ions. The maximum capacities of the monoliths with tertiary amine contents of 10, 20, 30, and 70 mol % for palladium(II) ions were 0.6, 1.1, 1.3, and 2.3 mmol/g, respectively. Darcy's permeabilities of water through the macroporous monolith were 10^?14 to 10^?13 m², and those were comparable to that through a commercially available membrane filter with a pore size of several micrometers. In the continuous‐flow process, the macroporous monolith with tertiary amine selectively adsorbed palladium(II) ions in the coexistence of copper(II) ions with 10 times higher concentration than the palladium(II) ions. The palladium(II) ions were eluted from the macroporous monolith, and the concentration of palladium(II) ions in the eluate was up to 45 times of that in the feed solution. The average enrichment factor and total recovery percentage of palladium(II) ions were 8.7 times and 95%, respectively. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134 , 44385.     

Influence of the metal centers of 2,6‐bis(imino)pyridyl transition metal complexes on ethylene polymerization/ oligomerization catalytic activities

Much work on bis(imino)pyridyl complexes with Fe(II) and Co(II) as ethylene polymerization catalysts has been reported in terms of designing new analogous ligands, while little work has been dedicated to the study of the effect of the metal center on catalyst performance. A series of bis(imino)pyridyl‐MCl₂ (M = Fe(II), Co(II), Ni(II), Cu(II), Zn(II)) transition metal complexes were synthesized, for which single crystals of the Co(II) and Cu(II) complexes were obtained. The crystal structures indicated that these complexes had similar coordination geometries. Being applied to ethylene polymerization at 25 °C and employing 500 equiv. of methylaluminoxane as co‐catalyst, the complexes with Fe(II), Co(II) and Ni(II) centers showed, respectively, catalytic activities of 1.25 × 10⁶ g (mol Fe)^?1 h^?1 Pa for ethylene polymerization, and 3.98 × 10⁵ g (mol Co)^?1 h^?1 Pa and 5.13 × 10³ g (mol Ni)^?1 h^?1 Pa for ethylene oligomerization. In contrast, the complexes with Cu(II) and Zn(II) centers were inactive. Crystal structure data showed that the coordination interactions provided a comparatively reliable quantification of the selectivity of the bis(imino)pyridyl ligand for the studied metal ions, which was in reasonable agreement with the Irving–Williams list. Moreover, for the Ni(II) and Cu(II) complexes, the strong coordination bonds and small N(imino)? M? N(imino) angles were unfavorable for several steps in the mechanism, such as ethylene coordination to the metal center, ethylene migratory insertion and olefin chain growth. All of these will reduce the speed of the overall reaction, indicating a decrease of catalytic efficiency in a given period. The poor activity of the Zn(II) complex for ethylene polymerization may be related to the reduction process by the alkylating agent. Copyright © 2010 Society of Chemical Industry