Synthesis and application of modified poly (styrene‐alt‐maleic anhydride) networks as a nano chelating resin for uptake of heavy metal ions

A chelating resin based on modified poly (styrene‐alt‐maleic anhydride) with 3‐aminobenzoic acid was synthesized. This modified resin was further reacted by 1,2‐diaminoethane or 1,3‐diaminopropane in the presence of ultrasonic irradiation to prepare tridimensional chelating resin for the removal of heavy metal ions from aqueous solutions. The adsorption behavior of Fe(II), Cu(II), Zn(II) and Pb(II) ions was investigated by synthesized chelating resins in various pH. Among the synthesized resins, CSMA‐AB1 and CSMA‐AB2 demonstrated a high affinity for the selected metal ions compared to SMA‐AB, and the order of removal percentage changes as follow: Fe(II) > Cu(II) > Zn(II) > Pb(II). The adsorption of all metal ions in acidic medium was moderate, and it was favored at the pH value of 6 and 7. Also, the prepared resins were examined for removal of metal ions from industrial wastewater and were shown to have a very efficient adsorption in the case of Cu(II), Fe(II) and Pb(II); however, the adsorption of Zn(II) was lower than others. The resin was characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction analysis and thermogravimetric analysis/derivative thermogravimetry. Copyright © 2012 John Wiley & Sons, Ltd.     

Synthesis and characterization of poly(styrene‐maleic anhydride)‐montmorillonite nanocomposite

Poly(styrene‐maleic anhydride)‐montmorillonite nanocomposites were prepared by intercalation of layered montmorillonite with the polymer ions. Synthetic approaches including polymerization and phosphonium salt formation have been used for polymer intercalation and dispersion of the host layers in the polymer matrix. The ratio of the mineral in the composites ranged 30–50%. Wide‐angle X‐ray diffraction (WAXD) disclosed that the d₍₀₀₁₎ spacing between the internal lamellar surface were only expanding to about 13 and 15 Å according to the type of phosphonium salt suggesting packing of polymer molecules between the layers. Examination of these materials by scanning and transmission electron microscopy showed spherical nano size particles of average diameter, 350 nm. Copyright © 2002 John Wiley & Sons, Ltd.     

Radiation synthesis and uranyl‐ion adsorption of poly(2‐hydroxyethyl methacrylate/maleic acid) hydrogels

A new kind of copolymeric hydrogel adsorbent containing hydrophilic groups that both provides swelling in water and chelates with uranyl ions was synthesized, and its adsorptive ability for recovering uranium from aqueous media was investigated. The uranyl adsorption capacities of poly(2‐hydroxyethyl methacrylate/maleic acid) hydrogels were determined with a polarographic technique to be 3.2–4.8 (mg UO/g dry gel) from a 15‐ppm uranyl nitrate solution at pH, 6 depending on the molar content of maleic acid in the hydrogel. Adsorption studies showed that other stimuli, the temperature, and the ionic strength of the solution also have important roles in the uranyl‐ion adsorption capacity of these hydrogels. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 39: 277–283, 2001     

Comparative study of electrostatic binding vs. complexation of Cu2+ ions with water‐soluble polymers containing styrene sulphonic acid and/or maleic acid units or their sodium salt forms

The interaction of Cu²⁺ ions with the homopolymer poly(styrene sulfonic acid) (PSSH), as well as with the copolymers of maleic acid (MAc) with styrene sulfonic acid (SSH) or vinyl acetate (VAc), was investigated in dilute aqueous solution through turbidimetry, potentiometry, viscometry, and spectrophotometry in the visible region. Cu²⁺ ions were introduced either through neutralization with Cu(OH)₂ of the acid form of the (co)polymers (PSSH, P(SSH‐co‐MAc) and P(VAc‐co‐MAc)) or through mixing of the sodium salt form of the (co)polymers (PSSNa, P(SSNa‐co‐MANa) and P(VAc‐co‐MANa)) with CuSO₄. Turbidimetry, potentiometry, and spectrophotometry revealed that the first carboxylic group of MAc or both carboxylate groups of MANa are involved in the complexation with Cu²⁺ ions when neutralization with Cu(OH)₂ or mixing with CuSO₄ are applied, respectively. The increased values of the reduced viscosity observed mainly at the first stages of neutralization of P(VAc‐co‐MAc) with Cu(OH)₂ indicate that interchain polymer‐Cu²⁺ complexation takes possibly place. Finally, the spectrophotometric behavior observed upon neutralization of P(SSH‐co‐MAc) with Cu(OH)₂ or mixing of P(SSNa‐co‐MANa) with CuSO₄ revealed that the strength of counterion binding by the sulfonate groups is, in fact, comparable with the complexation of Cu²⁺ ions with the carboxylate groups of MAc. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 1149–1158, 2008     

吲哚-3-乙酸与部分过渡金属离子M(Ⅱ)二元配合物的pH电位法研究

在25℃,I=0.10 mol/L KNO3的实验条件下,用pH电位法测定了吲哚-3-乙酸(IAA)在甲醇-水混合溶剂中的质子化常数,讨论了有机溶剂对质子化常数的影响,结果表明在实验范围内溶剂甲醇含量对质子化常数的影响呈线性关系.确定了二元体系M(Ⅱ)-IAA(M=Fe、Co、Ni、Cu、Zn和Cd)在甲醇含量为50%(V/V)的混合溶剂中主要存在的配合物物种,并测定了配合物的稳定常数.实验数据的处理运用计算机程序Hyperquad、Glee和Hyss完成.     

Structural and mechanical behavior of polypropylene/ maleated styrene‐(ethylene‐co‐butylene)‐styrene/sisal fiber composites prepared by injection molding

Hybrid composites consisting of isotactic poly(propylene) (PP), sisal fiber (SF), and maleic anhydride grafted styrene‐(ethylene‐co‐butylene)‐styrene copolymer (MA‐SEBS) were prepared by melt compounding, followed by injection molding. The melt‐compounding torque behavior, thermal properties, morphology, crystal structure, and mechanical behavior of the PP/MA‐SEBS/SF composites were systematically investigated. The torque test, thermogravimetric analysis, differential scanning calorimetric, and scanning electron microscopic results all indicated that MA‐SEBS was an effective compatibilizer for the PP/SF composites, and there was a synergism between MA‐SEBS and PP/SF in the thermal stability of the PP/MA‐SEBS/SF composites. Wide‐angle X‐ray diffraction analysis indicated that the α form and β form of the PP crystals coexisted in the PP/MA‐SEBS/SF composites. With the incorporation of MA‐SEBS, the relative amount of β‐form PP crystals decreased significantly. Mechanical tests showed that the tensile strength and impact toughness of the PP/SF composites were generally improved by the incorporation of MA‐SEBS. The instrumented drop‐weight dart‐impact test was also used to examine the impact‐fracture behavior of these composites. The results revealed that the maximum impact force (F_max), impact‐fracture energy (E_T), total impact duration (t_r), crack‐initiation time (t_init), and crack‐propagation time (t_prop) of the composites all tended to increase with an increasing MA‐SEBS content. From these results, the incorporation of MA‐SEBS into PP/SF composites can retard both the crack initiation and propagation phases of the impact‐fracture process. These prolonged the crack initiation and propagation time and increased the energy consumption during impact fracture, thereby leading to toughening of PP/MA‐SEBS/SF composites. © 2002 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 40: 1214–1222, 2002     

New potentially environmentally friendly copolymer of styrene and maleic acid—castor oil monoester

The maleic acid‐castor oil monoester (MACO) was synthesized and was used as monomer to synthesize a new potentially environmentally friendly copolymer of styrene and MACO (poly‐St/MACO) by suspension polymerization. Under the appropriate conditions, the poly‐St/MACO with yield of 81%, number average molecular weight of 44100 g/mol, and molecular weight distribution of 1.5 could be obtained. The chemical structures of the MACO and resulting copolymer were confirmed by Mass Spectrometry Infrared Spectroscopy and Nuclear Magnetic Resonance Spectroscopy H[1]. The results of thermogravimetric analysis and biodegradation test showed the poly‐St/MACO can be used as a new potentially environmentally friendly material with excellent thermal stability. Copyright © 2011 John Wiley & Sons, Ltd.     

Synthesis,characterization, and anti-tumor activities of some transition metal(II) complexes with podophyllic acid hydrazide

Four transition metal(II) complexes with podophyllic acid hydrazide (HL) were prepared and characterized by elemental analysis, complexometric titration, thermal analysis, conductivity, IR, and ¹H NMR. The complexes have the general formula ML₂ · nH₂O, where M = Zn, Cu, Co, and Ni, n = 2 or 0. Anti-tumor activities of podophyllotoxin, HL, ZnL₂ · ₂H₂O, and NiL₂ were tested by both the MTT and the SRB method. The results show that the activities of the complexes against the tumor cells tested are superior to HL and the anti-tumor activity of NiL2 is even similar to that of podophyllotoxin.     

Melt modification of poly(styrene‐co‐maleic anhydride) with alcohols in the presence of 1,3‐oxazolines

Various copolyesteramides were prepared by melt compounding at 220 °C involving reaction of poly(styrene‐co‐maleic anhydride), SMA, with 6, 17, and 28 wt % maleic anhydride content, and 1‐dodecanol, C12OH, in the presence of 2‐undecyl‐1,3‐oxazoline, C11OXA. Copolymer architectures were examined by means of ¹H NMR, FTIR, DSC, and TGA using model compounds prepared via solution reactions. While conversion of anhydride with alcohol was poor due to the thermodynamically favored anhydride ring formation, very high conversions were achieved when stoichiometric amounts of C11OXA were added. According to spectroscopic studies esteramide groups resulted from reaction of oxazoline with carboxylic acid intermediate. In the absence of alcohol, C11OXA reacted with anhydride to produce esterimides. Effective attachment of flexible n‐alkyl side chains via simultaneous reaction of C12OH and C11OXA resulted in lower glass‐transition temperatures of copolyesteramides. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1222–1231, 2000     

Branched poly(styrene‐b‐tert‐butyl acrylate) and poly(styrene‐b‐acrylic acid) by ATRP from a dendritic poly(propylene imine)(NH2)64 core

With the aim of creating highly branched amphiphilic block copolymers, the primary amine end groups of the poly(propylene imine) dendrimers DAB‐dendr‐(NH₂)₈ and DAB‐dendr‐(NH₂)₆₄ were converted to 2‐bromoisobutyramide groups. Poly (styrene‐b‐tert‐butyl methacrylate) (PS‐b‐PtBMA) was synthesized by ATRP from the eight end group initiator, and poly(styrene‐b‐tert‐butyl acrylate) (PS‐b‐PtBA) was synthesized from the 64 end group initiator. The tert‐butyl groups were removed to produce poly(styrene‐b‐methacrylic acid) (PS‐b‐PMAA) and poly(styrene‐b‐acrylic acid) (PS‐b‐PAA). Comparison of size exclusion chromatography (SEC) absolute molecular weight analyses of the polystyrenes with calculated molecular weights showed that the eight end group initiator produced a polystyrene with about eight branches, and that the 64 end group initiator produced polystyrene with many fewer than 64 branches. The PS‐b‐PtBA materials also have many fewer than 64 branches. The PS‐b‐PAA samples dissolved molecularly in DMF but formed aggregates in water even at pH 10. AFM images of the PS‐b‐PtBAs spin coated from THF and DMF onto mica showed aggregates. AFM images of the PS‐b‐PAAs spin coated from various mixtures of DMF and water at pH 10 showed flat disks and worm‐like images similar to those observed with linear PS‐b‐PAAs. Use of a PS‐b‐PAA and a PS‐b‐PMAA as templates for emulsion polymerization of styrene produced latexes 100–200 nm in diameter. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4623–4634, 2007     

Interpolymer complex between hydroxypropyl cellulose and maleic acid-styrene copolymer: phase behavior of semi-dilute solutions

The phase behavior of a water/hydroxypropyl cellulose/maleic acid-styrene copolymer (H2O/HPC/MAc-S) system was investigated in the semi-dilute range by turbidimetry, rheology, and optical microscopy. The two polymers under investigation form interpolymer complexes via hydrogen bonding. In the case of a total polymer concentration of cpol = 5 mg . mL(-1) a second phase segregates upon heating the homogeneous ternary system. By applying a constant shear rate (gamma = 50 s(-1)) the phase separation temperature of the system is 10-15 degrees C lower than for an unsheared one. For cpol = 10 mg . mL(-1) phase separation has already occurred at room temperature when the two binary polymer solutions are mixed. The distribution of the partners among the coexisting phases was examined by FT-IR spectroscopy. The stoichiometry of the interpolymeric complex (IPC) was estimated to be HPC/MAc-S = 40:60 (w/w) independent of cpol.     

Effects of divinylbenzene‐maleic anhydride copolymer hollow microspheres on crystallization behaviors,mechanical properties and heat resistance of poly(l‐lactide acid)

Divinylbenzene‐maleic anhydride copolymer hollow microspheres (DMs) were used as novel organic nucleating agents to promote crystallization of poly(l‐lactide acid) (PLLA). The effects of these DMs on crystal behaviors of the PLLA were investigated by differential scanning calorimeter (DSC), polarizing optical microscopy (POM), and wide angle X‐ray diffraction (WAXD). Both isothermal and non‐isothermal processes in DSC demonstrated that the DMs significantly altered the crystal behaviors of PLLA as both crystallization velocity and degree of crystallinity increased with increasing DM loadings from 0 to 3%. Our POM results also indicated that as nucleating agents, the DMs promoted nucleating densities and decreased spherulitic sizes. In addition, WAXD suggeted that the addition of DMs did not induce new types of crystals. Finally, our results showed that the ductility of the PLLA was enhanced by a small amount of DMs during the PLLA crystallization process since 0.5% DMs added to the PLLA resulted in 1.4‐fold increase in the elongation at break in comparision with the neat PLLA.     

Acrylonitrile–maleic anhydride copolymer membrane (II): effects of post‐treatment1

The effects of post‐treatment (including thermal treatment and base treatment) on the structure and performance of acrylonitrile–maleic anhydride (AN‐MA) copolymer membrane were investigated. The water flux decreased gradually (except the deviations when the temperature of thermal treatment was 50 °C or the time of thermal treatment was 50 min but rejection of bovine serum albumin increased slowly with increasing temperature or prolonging the time of thermal treatment. “The swelling effect of water in network” was proposed to explain the deviations. AN‐MA copolymer membrane is not resistant to a base. However, the performance of the membrane can be adjusted by treatment with a dilute base solution. Copyright © 2000 John Wiley & Sons, Ltd.     

Synthesis and metal complexation of dihydroxyphosphino‐functionalized crosslinked styrene/maleic anhydride copolymers

Crosslinked styrene (St)/maleic anhydride (MA) copolymers were synthesized, hydrolyzed with dicarboxylic acid, and converted to bear dihydroxyphosphino functionalities. The St–MA copolymers were prepared by azobisisobutyronitrile‐initiated polymerization in toluene at 90 °C in the presence of 2, 10, or 20% divinylbenzene crosslinker. The MA moiety was hydrolyzed into dicarboxylic acid to improve the hydrophilicity of the copolymers. The phenyl ring of St was phosphorylated with phosphorus trichloride in the presence of aluminum chloride and then hydrolyzed and oxidized with nitric acid at room temperature. The structures of the hydrolyzed and dihydroxyphosphino‐functionalized copolymers were confirmed by Fourier transform infrared spectroscopy and elemental analysis. The complexation behavior of these functionalized copolymers toward metal ions in 25 ppm aqueous solutions was observed over time periods of up to 7 h. The adsorption toward Pb(+2) was highest, followed by those of Cu(+2), Cr(+3), and Ni(+2). On the dihydroxyphosphino‐functionalized St–MA (20% divinylbenzene) copolymer, the adsorption of Pb(+2) showed a linear relationship with the concentrations and fit the Langmuir isotherm. The kinetics of Pb(+2) adsorption on this dihydroxyphosphino‐functionalized copolymer also fit the rate equation of the moving boundary model, t = [1 ? 3(1 ? X)^2/3 + 2(1 ? X)], where X is the fractional conversion. The metal‐ion adsorption kinetics of this copolymer appeared to be particle diffusion control, in which the moving boundary advanced from the surface toward the center. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 92–101, 2004     

Computing pKA values of hexa‐aqua transition metal complexes

Aqueous pK_A values for 15 hexa‐aqua transition metal complexes were computed using a combination of quantum chemical and electrostatic methods. Two different structure models were considered optimizing the isolated complexes in vacuum or in presence of explicit solvent using a QM/MM approach. They yield very good agreement with experimentally measured pK_A values with an overall root mean square deviation of about 1 pH unit, excluding a single but different outlier for each of the two structure models. These outliers are hexa‐aqua Cr(III) for the vacuum and hexa‐aqua Mn(III) for the QM/MM structure model. Reasons leading to the deviations of the outlier complexes are partially explained. Compared to previous approaches from the same lab the precision of the method was systematically improved as discussed in this study. The refined methods to obtain the appropriate geometries of the complexes, developed in this work, may allow also the computation of accurate pK_A values for multicore transition metal complexes in different oxidation states. © 2014 Wiley Periodicals, Inc.     

Swelling equilibria and dye adsorption studies of chemically crosslinked superabsorbent acrylamide/maleic acid hydrogels

Superswelling acrylamide (AAm)/maleic acid (MA) hydrogels were prepared by free radical polymerization in aqueous solution of AAm with MA as comonomer with some multifunctional crosslinkers such as trimethylolpropane triacrylate and 1,4-butanediol dimethacrylate. AAm/MA hydrogels were used in experiments on swelling and adsorption of a water-soluble monovalent cationic dye such as Basic Blue 17 (Toluidin Blue). As a result of dynamic swelling tests, the influence of relative content of MA on the swelling properties of the hydrogel systems was examined. AAm/MA hydrogels were swollen in the range 1660-6050% in water, while AAm hydrogels swelled in the range 780-1360%. Equilibrium water content of AAm/MA hydrogels were calculated in the range 0.8873-0.9837. Water intake of hydrogels followed a non-Fickian type diffusion. The uptake of the cationic dye, BB-17 to AAm/MA hydrogels is studied by batch adsorption technique at 25 °C. In the experiments of the adsorption equilibrium, S-type adsorption in Giles's classification system was found. The binding ratio of hydrogel/dye systems was gradually increased with the increase of MA content in the AAm/MA hydrogels.     

A thermodynamic analysis of specific interactions in homoblends of poly(styrene‐co‐4‐vinylpyridine) and poly(styrene‐co‐methacrylic acid)

Miscibility and strong specific interactions that occurred within homoblends of poly(styrene‐co‐4‐vinylpyridine) containing 15 mol % of 4‐vinylpyridine (PS4VP15) and poly(styrene‐co‐methacrylic acid) containing 15 mol % of methacrylic acid (PSMA15) have been examined by Fourier Transform infrared spectroscopy and DSC. The observed positive deviation of the glass transition temperature of the blends from the linear average line, was analyzed by the frequently used theoretical conventional approaches including the one very recently proposed by Brostow. A better fit was obtained when this latter is used. A reasonable agreement with experimental values was also obtained when the theoretical fitting parameter free method developed by Coleman, is applied to predict the composition dependence of the T_g of this system. A thermodynamic analysis of hydrogen bonding in this system was carried using the Painter‐Coleman association model and the variation of the Gibbs function of mixing and its different contributions and corresponding phase diagrams as a function of temperature and composition were estimated. This analysis predicted PSMA15 to be miscible with PS4VP15 in the whole composition range up to 150 °C. Above this temperature, a partial miscibility is predicted when the PS4VP15 is in excess. The DSC results are in agreement with these predictions. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 923–931, 2009     

Antibacterial activity of transition metal complexes containing a tridentate NNO phenoxymethylpenicillin‐based Schiff base. An anti‐MRSA iron (II) complex

Transition metal complexes containing a phenoxymethylpenicillin‐derived Schiff base (HL) 3 obtained from the condensation of phenoxymethylpenicillin (PMP) 1 , with 1,2‐diaminobenzene 2 , were prepared. Spectroscopic and physicochemical techniques, namely, UV–Vis, FT‐IR, ¹H‐NMR, EPR, mass spectrometry, magnetic susceptibility, molar conductance, DFT studies, together with elemental and thermal analyses were used to characterize the synthesized complexes. Based on the characterization studies, the general formulae [ML (OAc)(H₂O)₂] where M = Fe 4 , Co 5 , Ni 6 , Cu 7 , and Zn 8 , were proposed for the complexes. The Schiff base ligand 3 behaved as a monoanionic tridentate NNO chelating agent. On the basis of magnetic and spectral data an octahedral geometry for all the complexes was suggested. Schiff base ligand 3 , and the metal complexes 4 – 8 were tested against G(+) or bactericidal activity by agar disc diffusion method and minimal inhibitory concentration (MIC). The results were compared with the activity of the standard drug PMP 1 . In vitro bacterial viability revealed that 3  had similar activity than 1 and exhibited modification in its bactericidal activity when formed metal complexes. It was found that the complexes 4 , 6 and 7 exhibited much better bactericidal activity than 1 against methicillin‐resistant Staphilococcus Aureus (MRSA) being complex 4 the most promising compound showing a MIC value of 0.042 μmol/ml.     

Multifunctional,water‐soluble,C60‐pendant maleic anhydride copolymer

Starting from the synthesis of a new methanofullerene derivative bearing an alcohol group, we report on the preparation of a water‐soluble, fullerene‐pendant copolymer. This multifunctional, C₆₀‐pendant maleic anhydride copolymer was characterized by conductometric titration, Fourier transform infrared and ultraviolet spectroscopy, thermogravimetric analysis, and cyclic voltammetry. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 5814–5822, 2005     

Phase behavior and Li+ Ion conductivity of styrene‐ethylene oxide multiblock copolymer electrolytes

Solid polymer electrolytes are attractive materials for use as battery separators. Here, a molecular weight series of polystyrene–polyethylene oxide (PEO) multiblock copolymers was synthesized by the thiol–norbornene click reaction. The subsequent materials were characterized both neat and with a lithium bis‐(trifluoromethane)sulfonimide salt loading [(Li)/(EO)] of 0.1. In general, neat samples demonstrated crystallinity scaling with PEO content. Lithium ion‐containing samples had broad scattering peaks, half of which displayed disordered scattering, even at the lowest block molecular weights (polystyrene = 1 kg/mol, PEO = 1 kg/mol). Fitting of disordered scattering data, using the random phase approximation, yielded χ_RPA and R_g values that were compared with recent predictive work by Balsara and coworkers. The predictions were accurate near the volume fraction f_PEO = 0.5 but deviated symmetrically with volume fraction asymmetry. Samples were also analyzed by electrochemical impedance spectroscopy for their potential to conduct lithium ions. Samples with f_PEO ≥ 0.5 demonstrated robust conductivity, whereas samples below this volume fraction conducted very poorly, with one exception (f_PEO = 0.24). This work expanded upon our recently reported approach to multiblock copolymer synthesis, demonstrating the improved access of materials to further our fundamental understanding of multiblock copolymers. Copyright © 2016 John Wiley & Sons, Ltd.