Copolymers of acrylic acid with 2‐acryloyloxyethyl 2,4‐dichlorophenoxyacetate: Synthesis and herbicide release

Free‐radical copolymerization of acrylic acid with 2‐acryloyloxyethyl 2,4‐dichlorophenoxyacetate using 1.0 mol/L 1,4‐dioxane solution and 1.5 × 10^?2 mol/L of 2,2′ azobisisobutyronitrile as initiator has been carried out at 50°C. In addition to low conversion solution experiments performed to estimate the monomer reactivity ratios, three different copolymerizations over the whole range of conversions have been made. Theoretical values of cumulative copolymer composition, determined by the Mayo‐Lewis terminal model, have been correlated with those experimentally obtained. Finally, the herbicide release in three different aqueous pH buffer solutions has been evaluated in heterogeneous phase. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4238–4244, 2006     

A net draft tube slurry airlift bioreactor for 2,4‐D (2,4‐dichlorophenoxyacetic acid) pesticide biodegradation

Biodegradation of the pesticides 2,4‐D have been investigated in a net draft tube airlift bioreactor at different concentrations (10–160 ppm) and air flow rates (0.75–4 L min^?1), employing acclimatised activated sludge. A modification for the glass draft tube airlift bioreactor was proposed in which the draft tube is made of non‐woven polypropylene textile net. The experiments were carried out as well in a bubble column (BC) for comparison. The results confirmed that immobilising the activated sludge on the net of the draft tube could enhance the substrates mass transfers and improve the biodegradation rate. A mathematical model was developed to simulate the biodegradation process. The simulated results were in good agreement with the experiments.     

Graft copolymerization of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto carboxymethylcellulose (sodium salt) by H2O2/Fe+2 redox pair

The effect of the reaction conditions on the grafting parameters during grafting of 2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid onto sodium carboxymethylcellulose using H₂O₂/Fe⁺² redox pair are studied at 30°C. The grafting ratio, add on, and conversion initially increase with the H₂O₂ concentration in the range of (10.0–15.0) × 10^?2 mol dm^?3. Thereafter, these parameters decrease with the H₂O₂ concentration. The grafting ratio, add on, and conversion increase when increasing the ferrous ion concentration from (0.5 to 4.0) × 10^?2 mol dm^?3 and decrease with a further increase in the concentration. It is observed that the grafting ratio and add on increase with the monomer concentration, whereas the conversion decrease. The hydrogen ions seem to be facilitating the grafting reaction up to a certain concentration and after this concentration seem to be retarding the process. The grafting ratio, add on, and conversion decrease with the sodium carboxymethylcellulose concentration. When increasing the time period from 60 to 90 min, the grafting parameters increase but decrease thereafter. Similarly, when increasing the temperature from 25 to 30°C, the grafting parameters increase and decrease thereafter. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 4819–4825, 2006     

Catalytic synthesis of toluene‐2,4‐diisocyanate from dimethyl carbonate

The process for catalytic synthesis of toluene‐2,4‐diisocyanate (TDI) from dimethyl carbonate (DMC) consists of two steps. Starting from the catalytic reaction between toluene‐2,4‐diamine (TDA) and DMC, dimethyl toluene‐2,4‐dicarbamate (TDC) is formed, and then decomposed to TDI. For the first step, the yield of TDC is 53.5% at a temperature of 250 °C, over Zn(OAc)₂/α–Al₂O₃ catalyst. For the second step, the yield of TDI is 92.6% at temperatures of 250–270 °C and under pressure of 2.7 kPa, over uranyl zinc acetate catalyst, when di‐n‐octyl sebacate(DOS) is used as heat‐carrier, and a mixture of tetrahydrofuran (THF) and nitrobenzene is used as solvent. © 2001 Society of Chemical Industry     

Synthesis of ternary copolyamides from aromatic diamine (m‐phenylenediamine,diaminodiphenylsulfone), aromatic diamine with carboxyl or sulfonic group (3,5‐diaminobenzoic acid, 2,4‐diaminobenzenesulfonic acid), and iso‐ or terephthaloyl chloride

The copolymerization of iso‐ or terephthaloyl chloride, m‐phenylenediamine or diaminodiphenylsulfone, and 3,5‐diaminobenzoic acid or 2,4‐diaminobenzene sulfonic acid (or sulfonate) was studied. Copolymers with high reduced viscosity could be obtained by low temperature solution polymerization, but not by interfacial polymerization. The reduced viscosity of the copolyamides obtained was dependent upon the species of the aromatic diamine compounds and the acid acceptors used. Low temperature solution copolymerization with the comonomer 3,5‐diaminobenzoic acid should be done without acid acceptors, because acid acceptors cause gelation. With 2,4‐diaminobenzenesulfonic acid or 2,4‐diaminobenzenesulfonate, pyridine or triethylamine as acid acceptors give polymers with higher reduced viscosity. The flat asymmetric membranes of the copolyamides prepared from terephthaloyl dichloride and mixed diamine components of 3,3′‐diaminodiphenylsulfone and 3,5‐diaminobenzoic acid showed not only good reverse osmosis performance, but also high chlorine resistance. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 913–920, 2000     

Electrical/pH responsive properties of poly(2‐acrylamido‐2‐methylpropane sulfonic acid)/hyaluronic acid hydrogels

Poly(2‐acrylamido‐2‐methylpropane sulfonic acid) (PAMPS)/hyaluronic acid (HA) interpenetrating polymer network (IPN) hydrogels have been prepared by using the sequential‐IPN method. The IPN hydrogels exhibited swelling behavior in solutions at various pHs, in NaCl solutions, and under electrical DC stimulation. The IPN hydrogels were highly swollen in water, but lost much of their water capacity when transferred to solutions having a high ionic strength. The IPN hydrogels showed a significant responsive deswelling in an applied electric field. This behavior indicates the potential application of IPN hydrogels as biomaterials. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 1731–1736, 2004     

Preparation of polystyrene/toluene‐2,4‐ di‐isocyanate–modified montmorillonite hybrid

A novel selective interlamellar modification of cetyltrimethylammonium bromide‐exchanged montmorillonite (MMT) by toluene‐2,4‐di‐isocyanate (TDI) has been successfully obtained, and a polystyrene/TDI‐modified MMT hybrid has been prepared. After the interlamellar modification, TDI was grafted to hydroxyl groups of the MMT, and the orientation of cetyltrimethylammonium in the interlayer space changed from a bilayer lying flat structure to a double‐layer inclined one. The structures of the TDI‐modified MMT and the hybrid were characterized by Fourier transform infrared (FTIR) spectra, powder X‐ray diffraction (XRD), and transmission electron microscopy (TEM) techniques. A schematic model of the TDI‐modified MMT structure was also presented. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 2201–2205, 2000     

Oxidation of benzothiazole, 2‐mercaptobenzothiazole and 2‐hydroxybenzothiazole in aqueous solution by means of H2O2/UV or photoassisted Fenton systems

Oxidative treatments of benzothiazole and benzothiazole derivatives (2‐mercaptobenzothiazole, 2‐hydroxybenzothiazole) in aqueous solution have been studied by using H₂O₂/UV and iron(III) photoassisted Fenton techniques. Experimental runs have been carried out in the pH range 3.0 –8.0 by means of annular reactors and proper UV lamps. The effect of pH, the initial concentration of hydrogen peroxide, the substrate, and the iron(III) concentrations have been investigated. A suitable model has been developed and used for the best estimation of kinetic constants for HO radical attack on the target molecules with the H₂O₂/UV system. The values obtained with this model are consistent with those reported in the literature for other heterocyclic compounds. © 2001 Society of Chemical Industry     

Thermodynamic modeling of HNO3‐H2SO4‐H2O ternary system with symmetric electrolyte NRTL model

The nitric acid concentration/sulfuric acid concentration (NAC/SAC) process has been widely used for concentrating dilute aqueous nitric acid and recovering spent sulfuric acid. Dilute nitric acid (65 to 80 wt %) is concentrated using sulfuric acid to bind water and break the nitric acid‐water azeotrope at approximately 68 wt % nitric acid. To support heat and mass balance calculations and process simulation for NAC/SAC processes, we develop a comprehensive thermodynamic model for nitric acid‐sulfuric acid‐water ternary system based on previously published thermodynamic models of nitric acid‐water and sulfuric acid‐water binary systems with eNRTL equation. The ternary system model correlates well the isobaric vapor‐liquid equilibrium data at one atmosphere and the water and nitric acid activities data at 273.15 K for the ternary. Contour plots of boiling points, vapor phase composition, and specific heat capacity of the ternary system, as well as a Merkel enthalpy‐concentration chart are generated for engineering use. © 2017 American Institute of Chemical Engineers AIChE J, 63: 3110–3117, 2017     

Asymmetric Organocatalytic Cascade Michael/Hemiketalization/Retro‐Aldol Reaction of 2‐[(E)‐2‐Nitrovinyl]phenols with 2,4‐Dioxo‐4‐arylbutanoates: A Convenient Access to Chiral α‐Keto Esters

An unprecedented organocatalytic enantioselective cascade Michael/hemiketalization/retro‐aldol reaction of 2‐[(E)‐2‐nitrovinyl]phenols and 2,4‐dioxo‐4‐arylbutanoates is described. With a bifunctional squaramide catalyst incorporating (1R,2R)‐1,2‐diphenylethane‐1,2‐diamine, the reactions afford products in 75–99% yields with 80–98% ee. This process provides an enantioselective pathway for the synthesis of chiral α‐keto esters, precursors of 3‐arylproline derivatives, δ‐amino α‐keto acids or cyclic α‐keto lactams.

     

Kinetics,degradation pathway and reaction mechanism of advanced oxidation of 4‐nitrophenol in water by a UV/H2O2 process

Photooxidation of 4‐nitrophenol (4‐NP) in water by the UV/H₂O₂ advanced oxidation process was carried out in order to investigate the kinetics and pathway of 4‐NP degradation. The experimental results showed that the photodegradation of 4‐NP accorded well with pseudo‐first order kinetics. The effects of different parameters, such as H₂O₂ dosage, pH value and various anion scavengers on the degradation of 4‐NP have been investigated in detail. It was found that acidic conditions are more favorable to the degradation of 4‐NP but many anions, such as HCO₃^?, NO₃^? and Cl^?, slow down the photooxidation rate of 4‐NP. Hydroquinone, 1,2,4‐trihdroxybenzene, 4‐nitropyrogallol, and 4‐nitrocatechol were tentatively identified as the intermediates of 4‐NP degradation by GC/MS after samples were derivatized by N,O‐bis(trimethylsilyl)‐trifluoroacetamide (BSTFA). A degradation pathway was proposed to account for the observed intermediates produced during 4‐NP degradation by the UV/H₂O₂ process. Copyright © 2003 Society of Chemical Industry     

Proton conducting polymer blends from poly(2,5‐benzimidazole) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid)

Proton conducting polymer electrolyte membranes were produced by blending of poly(2,5‐benzimidazole) (ABPBI) and poly(2‐acrylamido‐2‐methyl‐1‐propanesulfonic acid) (PAMPS) at several stoichiometric ratios with respect to polymer repeating units. The membranes were characterized by using Fourier transform infrared spectroscopy for interpolymer interactions and scanning electron microscope for surface morphology. Thermal stability of the materials was investigated by thermogravimetric analysis. Glass transition temperatures of the samples were measured via differential scanning calorimetry. The spectroscopic measurements and water uptake studies indicate a complexation between ABPBI and PAMPS that inhibited polymer exclusion up on swelling in excess water. Proton conductivities of the anhydrous and humidified samples were measured using impedance spectroscopy. The proton conductivity of the humidified ABPBI:PAMPS (1 : 2) blend showed a proton conductivity of 0.1 S/cm, which is very close to Nafion 117, at 20°C at 50% relative humidity. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Anthranilic acid assisted preparation of Fe3O4–poly(aniline‐co‐o‐anthranilic acid) nanoparticles

Magnetic Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles were prepared by a novel and simple method: anthranilic acid assisted polymerization. The synthetic strategy involved two steps. First, Fe₃O₄ nanoparticles capped by anthranilic acid were obtained by a chemical precipitation method, and then the aniline and oxidant were added to the modified Fe₃O₄ nanoparticles to prepare well‐dispersed Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles. Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles exhibited a superparamagnetic behavior (i.e., no hysteresis loop) and high‐saturated magnetization (M_s = 21.5 emu/g). The structure of the composite was characterized by Fourier‐transform infrared spectra, X‐ray powder diffraction patterns, and transmission electron microscopy, which proved that the Fe₃O₄–poly(aniline‐co‐o‐anthranilic acid) nanoparticles were about 20 nm. Moreover, the thermal properties of the composite were evaluated by thermogravimetric analysis, and it showed excellent thermal stability. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1666–1671, 2006     

Poly‐2‐oxazolidones with tailored physical properties synthesized by catalyzed polyaddition of 2,4‐toluene diisocyanate and different bisphenol‐based diepoxides

In the current study, we investigated poly‐2‐oxazolidones containing one of four different diglycidyl ethers carrying different bulky bisphenol centers. With increasing steric hindrance of the bisphenol‐based diepoxide from bisphenol F to bisphenol A, Z and TMC, the glass transition temperature (T_g) increased markedly from 156 to 211 °C, whereas the plateau modulus of the polymer, i.e. the chain flexibility as determined from rheological characterization, remained almost unchanged. This study demonstrates the general feasibility of the chemical design of poly‐2‐oxazolidones as an amorphous high‐performance thermoplastic. © 2016 Society of Chemical Industry     

Cure reaction of multi‐walled carbon nanotubes/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites: effect of carboxylic functionalization of MWCNTs

BACKGROUND: The aim of this work was to study, using differential scanning calorimetry, the effect of carboxylic functionalization of multi‐walled carbon nanotubes (MWCNTs) on the cure reaction of MWCNTs/diglycidyl ether of bisphenol A/2‐ethyl‐4‐methylimidazole (MWCNTs/DGEBA/EMI‐2,4) nanocomposites. This is important for the practical design, analysis and optimization of novel materials processing. RESULTS: Comparing the influence of non‐functionalized MWCNTs and carboxyl‐functionalized MWCNTs, it was found that, at the initial curing stage, both MWCNTs act as catalyst and COOH functionalization of MWCNTs has a catalytic effect on the curing process. Then, at the later curing stage, non‐functionalized MWCNTs prevent the occurrence of vitrification, whereas COOH functionalization of MWCNTs promotes vitrification. Non‐functionalized MWCNTs decrease the degree of curing, as evidenced by lower total heat of reaction and lower glass transition temperatures of nanocomposites compared to neat epoxy; however, COOH functionalization of MWCNTs increases the degree of curing. CONCLUSION: For the development of composites, COOH functionalization of MWCNTs could bring a positive influence to the composite process. Its acceleration of cure could help shorten pre‐cure time or lower pre‐treatment temperature, and its effect of promoting vitrification could help shorten post‐cure time or lower post‐treatment temperature. Copyright © 2009 Society of Chemical Industry     

Biodegradation of 2,4-dichlorophenoxy acetic acid (2,4-d) by pseudomonas cepacia: Stoichiometric study

Pseudomonas cepacia biodegraded 2,4-dichlorophenoxyacetic acid (2,4-D) according to the following stoichiometric equation: C₈ H₆ Cl₂ O₃ + c₁ O₂ + c₂ NH₃ → c₃ CH_x N_z O_y + c₄ CO₂ + c₅ H₂ O + c₆ Cl_? + c₇ REIM where CH_x N_z O_y represents the bacterial cells and REIM is the residual extracellular intermediate metabolites. The stoichiometric coefficients c₁ to c₇ were determined from C, N, O, H and Cl balances together with the experimental data on the biodegradation of ¹⁴ C-carboxy-labeled-2,4-D and ¹⁴ C-ring-uniformly-labeled-2,4-D. The stoichiometric equation obtained predicted satisfactorily the total oxygen consumption for and the total heat production from the biodegradation of 2,4-D for a wide range of initial concentrations from 80 to 500 mg/L.     

Accelerating effect of NaNO2 on the polymer plating of 6‐substituted‐1,3,5‐triazine‐2,4‐dithiol mono sodium salts

Organic polymer plating properties of 6‐substituted‐1,3,5‐triazine‐2,4‐dithiol mono sodium salts were investigated in the presence of various supporting electrolytes. Among these, the NaNO₂ supporting electrolyte greatly accelerated the film formation rate in polymer plating. The accelerating effect of NaNO₂ was further confirmed by comparing plating potentials in the presence of NaNO₂ and Na₂CO₃. The potentiostatic polymer plating of DAN in the presence of the NaNO₂ supporting electrolyte took place in the potential range of 1.65–1.8 V (compared against saturated calomel electrode reference). Film formation was influenced by such factors as the pH of solution and both the chemical structure and the concentration of triazine dithiol. In polymer platings, NO anions are thought to be electrochemically oxidized to yield NO radicals and these radicals react with DAN to yield new thiyl radicals. The thiyl radicals in the DAN molecules couple with each other by means of disulfide bonds, resulting in the growth of polymer film. Organic polymer plating films are shown to contain disulfide bonds, monosulfide bonds obtained by the reaction between allyl groups and thiyl radicals, and network chains. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 82: 2300–2309, 2001     

Synthesis of 4‐Aryl‐2(5H)‐furanones by Gold(I)‐Catalyzed Intramolecular Annulation

A novel method that involves intramolecular annulation and a new type of rearrangement has been developed for the synthesis of 4‐aryl‐2(5H)‐furanones. A variety of prop‐2‐ynyl 3‐oxo‐3‐phenylpropanoates undergo annulation cyclization in the presence of chloro(triphenylphosphine)gold and trifluoromethanesulfonic to afford the desired products in moderate to high yields.     

Solubility and metastable zone width measurement of 2,4-diaminobenzenesulfonic acid in (H2SO4 + H2O) system

The equilibrium solubility of 2,4-diaminobenzenesulfonic acid and super solubility as well as metastable zone width were measured in (H₂SO₄ + H₂O) system by the laser dynamic method at elevate temperature range from 298.15 K to 338.15 K. 2,4-Diaminobenzenesulfonic acid solubility dependence on the temperature and solvent composition were correlated by the modified Apelblat equation, (CNIBS)/Redlich-Kister model and Jouyban-Acree model. The correlated results by three correlation models were in good accord with the experimental values according to relative average deviations (RD), root-mean-square deviations (RMSD), and correlation coefficients (R²). The metastable zone width increased with temperature and sulfuric acid content. The dissolution enthalpy, dissolution entropy and the Gibbs energy were calculated from the experimental values, which indicated that dissolution process of the 2,4-diaminobenzenesulfonic acid was endothermic. The solubility and calculation models of 2,4-diaminobenzenesulfonic acid in (sulfuric acid + water) system could provide the basic data to the crystallization and purifying of the 2,4-diaminobenzenesulfonic acid.