Corrosion inhibition of zinc-plated steel in 0.5, 1 and 1.5 M sulphuric acid by poly(ethylene glycol)

The effect of poly(ethylene glycol) (PEG) 4000 on the corrosion of zinc-plated steel in H₂SO₄ has been investigated over a wide range of conditions. It was found that the corrosion rate depends upon exposure time. The rate of corrosion goes down rapidly to reach a low value, which is an almost constant value within 5 hr under most conditions. This trend was also found by Growock and Lopp for the inhibition of steel corrosion in HCl with 3-phenyl-2-propyl-1-ol. Other workers have linked this slow fall-off in the corrosion rate to film formation. The corrosion rate was found to decrease slowly with increasing PEG concentration, and to increase slowly with acid concentration for all conditions. The effect of temperature on corrosion rate was found to be similar to that of acid concentration. The corrosion rate decreased exponentially with poly(ethylene glycol) concentration. The percentage inhibition reached a value of 48.93 for a PEG concentration of 4 ppm: to double this, the concentration had to be increased to 40,000 ppm. Sulphuric acid titration against sodium hydroxide showed no change in acid concentration during the corrosion protection process, thus supporting the film protection theory     

Formation and cure of novolacs: NMR study of transient molecules

High-resolution magnetic resonance spectroscopy has been used to investigate three areas of novolac resin chemistry: first, the lifetimes of glycol species in formalin under acid and base conditions and the reactivity of methylene glycol towards alcohols; second, the in situ identification of novolac resin intermediates; third, the novolac–hexamethylenetetramine cure mechanisms. It is shown that the mean lifetime of a given glycol species is an order of magnitude shorter under basic conditions than under an acid of equal normality. The ratio of the equilibrium constants for the addition of methylene glycol to methanol, benzyl alcohol, and phenol was measured as 70:20:1. New reactive intermediates were discovered while monitoring the reaction of phenol and formalin. The reactions of various phenols with hexamethylenetetramine were studied, and short-lived benzoxazines were detected at 100–120°C whenever ortho hydrogen was available on the phenolic nucleus. The NMR peak assignments in the reaction sequence: benzoxazine, dibenzylamine, tribenzylamine, diphenylmethane are presented. Spectra of the very elusive p-benzylamines of 2,6-xylenol were recorded at 100–155°C. At 170°C, the lifetimes of these p-benzylamines are too short to afford proton resonance spectra. No evidence of hexahydrotriazine or (CH₂ = N-CH₂)₃N type structures was found in 100 MHz NMR spectra of reaction mixtures of a phenol and hexamethylene-tetramine.     

KINETICS AND PHASE TRANSFORMATIONS DURING THE REACTION OF NaCl-SODALITE IN AMMONIUM CHLORIDE SOLUTIONS

The reaction behavior of sodium chloride sodalite Na₈[AlSiO₄]₆Cl₂ in ammonium chloride solution has been investigated under mild hydrothermal conditions (T = 473 K) for reaction times up to 72 h. Reactions under weak acid conditions led to an amorphous aluminosilicate phase comparable to a leaching process. This material forms an amorphous layer around the sodalite grains, preventing the framework from further decomposition. About 52% of sodalite was damaged by acid leaching after 11 hours and this amount remains nearly constant even at longer reaction periods up to 72 hours. Cation exchange was observed in sodalite only on a very low level (< 10%). Beside these reactions under acid conditions (pH » 5) some additional experiments in alkaline solutions were done to improve ion exchange of sodalite. Thus an ammonium/ammonia buffer solution was used (pH » 9) at various temperatures in a range of 353 – 473 K. Neither cation exchange nor decomposition of the sodalite was obtained at 353 and 393 K after 72 hours. Formation of amorphous material started at 433 K. In contrast to the acid conditions a total transformation of sodalite into a crystalline ammonium aluminosilicate phase was observed at 473 K.     

Simple formylacetal (CH2) as a novel linker for saccharide synthesis on soluble-polymer support

Described herein is a new formylacetal (CH₂) linker for immobilization of small molecules onto a soluble-polymer support, poly(ethylene glycol) ω-monomethyl ether (MPEG), and its application to saccharide synthesis. This small linker allows immobilization of a hindered hydroxy group such as the 4-hydroxy group of glucose onto MPEG. The linker is stable under several reaction conditions including glycosylation. Removal of this support was found to be achieved through cleavage of the CH₂ linker either by a Lewis acid (TMSI or Ce(OTf)_x) or a Brønsted acid (trifluoroacetic acid) in moderate to good yields. In combination with solid acid catalyst, simpler operations became possible during the working-up and purification processes.     

Bifunctional Onium and Potassium Iodides as Nucleophilic Catalysts for the Solvent-Free Syntheses of Carbonates,Thiocarbonates, and Oxazolidinones from Epoxides

The catalytic potential of organo-onium iodides as nucleophilic catalysts is aptly demonstrated in the synthesis of cyclic carbonates from epoxides and carbon dioxide (CO₂), as a representative CO₂ utilization reaction. Although organo-onium iodide nucleophilic catalysts are metal-free environmentally benign catalysts, harsh reaction conditions are generally required to efficiently promote the coupling reactions of epoxides and CO₂. To solve this problem and accomplish efficient CO₂ utilization reactions under mild conditions, bifunctional onium iodide nucleophilic catalysts bearing a hydrogen bond donor moiety were developed by our research group. Based on the successful bifunctional design of the onium iodide catalysts, nucleophilic catalysis using a potassium iodide (KI)-tetraethylene glycol complex was also investigated in coupling reactions of epoxides and CO₂ under mild reaction conditions. These effective bifunctional onium and potassium iodide nucleophilic catalysts were applied to the solvent-free syntheses of 2-oxazolidinones and cyclic thiocarbonates from epoxides.     

Kinetics and mechanism of decarboxylation of aspartic acid with ninhydrin

The kinetic study of the decarboxylation of aspartic acid has been carried out at various [ninhydrin], [H⁺] and at different temperature ranging from 60–95°C. The reaction follows an irreversible first-order reaction path under pseudo first-order kinetic conditions. The variation of pseudo first-order rate constant (k_obs) with ninhydrin concentration was found to be in agreement with equation 1/k_obs = B₁ + B₂/[Ninhydrin]. One mol of carbondioxide evolved from decarboxylation of α-COOH and second mol of carbondioxide comes from the decarboxylation of β-keto acid which is an intermediate and formed during the course of ninhydrin and aspartic acid reaction. On the basis of the observed data, a possible mechanism has been proposed.     

PEG 400 promoted nucleophilic substitution reaction of halides into organic azides under mild conditions

Abstract

Polyethylene glycol 400 (PEG 400) has been demonstrated as an efficient and eco-friendly reaction medium for the preparation of organic azides from structurally diverse halides by nucleophilic substitution reaction with NaN₃ under mild conditions. The advantages of this protocol are: operational simplicity, environmental safety, broad substrate scope, excellent functional group tolerance, and short reaction time. The PEG 400 can be recovered and reused.     

Microwave-assisted lipase-catalyzed synthesis of polyethylene glycol stearate in a solvent-free system

Polyethylene glycol stearate, a condensation esterification product of stearic acid and polyethylene glycol 600, was widely applied in the biomedical and healthcare industries. The current work focuses on the enzymatic synthesis of PEG stearate using CALB_ex10000, a commercial Lipase enzyme in solvent-free conditions using microwave irradiation. The influence of various reaction parameters such as temperature, molar ratio of reactants, and enzyme loading was studied to obtain the highest conversion. Maximum conversion of 85% was attained under molar ratio 1:1 (PEG 600 to stearic acid using 0.7% (w/w) enzyme loading at 60 ​°C of temperature in 70 ​min of reaction time. Further, the thermodynamic parameters were analyzed and compared with the conventional and ultrasound-assisted synthesis of PEG stearate. The enzyme was recycled up to 5^th cycle giving more than 35% of the initial activity.     

Microwave-assisted NaHSO4-catalyzed synthesis of ricinoleic glycol ether esters

The synthesis of several ricinoleic acid glycol ether esters by high-pressure microwave radiation is described. Ricinoleic acid which is from castor oil reacted fastly with glycol ethers in the presence of NaHSO₄?·?H₂O and dichloromethane (DCM) in special microwave reactor. The influences of reaction factors such as catalyst and solvent type, reaction temperature, and time were investigated and the optimal reaction conditions were obtained. The activity of catalyst had a higher performance up to the 10th cycle and the excellent values of turnover numbers and turnover frequency were obtained. Compared with the traditional esterification in reflux heating systems., the microwave-assisted process has many advantages such as shorter reaction time, less side effects, higher yield, which is a great potential for the development of green chemistry.     

PEG‐DIL‐based MnCl42−: A novel phase transfer catalyst for nucleophilic substitution reactions of benzyl halides

Poly(ethylene glycol) dicationic ionic liquid‐based MnCl₄^2? was prepared by nucleophilic substitution of poly(ethylene glycol) dichloride with methylimidazole followed by reaction with MnCl₂. The structural properties of the catalyst were systematically investigated using Fourier transform infrared, UV–visible and Raman spectra and thermogravimetric analysis. The application of this catalyst allows the synthesis of a variety of benzyl thiocyanates and azides in high yield under reflux conditions in water. The main advantages of this method are its easy nature, rapidity, environmental benignity and high yields.     

NMR.-Investigation of the Formaldehyde Addition and Oligomerisation Equilibria in the System Formaldehyde/Water/Acetic Acid/Hydrochloric Acid

An NMR. investigation of the state of formaldehyde in acidic solutions has been carried out. Solutions of DCl/D₂O/CD₃COOD containing two sources of formaldehyde, i.e. paraformaldehyde (I) and trioxane (II), were used for this purpose. In systems I and II the effect of various D₂O/CD₃COOD ratios, at a constant DCl concentration, was studied, while for II the effect of changing DCl concentration was also investigated. The results show that in aqueous solution, formaldehyde exists primarily as the monomeric and linear oligomeric forms of methylene glycol. Reducing the amount of D₂O (at constant DCl concentration), while increasing the CD₃COOD content, results in an increase in the polymeric species and in trioxane. In addition, substitution of water by acetic acid results in systems that are catalytically more active than aqueous solutions of the same hydrochloric acid concentration. Along with the usual polymer-monomer equilibria which exist in such solutions, side reactions of methylene glycol with the hydrochloric acid present also occur to a small extent, e.g. acetylation, substitution of OH by Cl and the Cannizzaro reaction. It is suggested that these findings will result in a better understanding of the formaldehyde crosslinking reactions in cotton cellulose.     

Fast and Tight Boronate Formation for Click Bioorthogonal Conjugation

A new click bioorthogonal reaction system was devised to enable the fast ligation (k_ON≈340 m ^?1 s^?1) of conjugatable derivatives of a rigid cyclic diol (nopoldiol) and a carefully optimized boronic acid partner, 2‐methyl‐5‐carboxymethylphenylboronic acid. Using NMR and fluorescence spectroscopy studies, the corresponding boronates were found to form reversibly within minutes at low micromolar concentration in water, providing submicromolar equilibrium constant (K_eq≈10⁵–10⁶ m ^?1). Efficient protein conjugation under physiological conditions was demonstrated with model proteins thioredoxin and albumin, and characterized by mass spectrometry and gel electrophoresis.     

Supercritical carbon dioxide assisted synthesis of amphiphilic graft copolymers based on poly(styrene-co-maleic anhydride) with methoxyl poly(ethylene glycol) side chains

Supercritical carbon dioxide（scCO₂） was used as a reaction medium in synthesizing amphiphilic graft copolymers composed of poly（styrene-co-maleic anhydride）（SMA） backbones and methoxyl poly（ethylene glycol）（MPEG） side chains via esterification.The synthesized copolymers were characterized by Fourier transform infrared spectroscopy（FTIR）,gel permeation chromatography（GPC）,¹H-NMR,thermo-gravimetric analysis（TGA） and differential scanning calorimetric analysis（DSC）.The gelation phenomenon was suppressed effectively by tuning reaction conditions.The influences of scCO₂ temperature and pressure on the conversion of anhydride were investigated.It was found that the highest conversion ratio occurred at 80℃under a constant pressure of 14 MPa or 26 MPa.With the increase of scCO₂ pressure,the conversion ratio increased first,and then leveled off.The conversion ratio of anhydride could be controlled by regulating the reaction conditions.It was also revealed that using low molecular weight MPEG brought a high conversion ratio of anhydride.     

Kinetics of dissociation of tris-2,2′-bipyridyl-iron(II) cation in aqueous acetic acid solutions

The kinetics of dissociation of tris-2,2′-bipyridyl-iron(II) complex ion have been examined in aqueous acetic acid solutions. The reaction is first order in the complex ion; the dependence of rate on H⁺ is somewhat like that observed in aqueous solutions approaching a limiting value at higher H⁺ concentrations. The influence of solvent composition on the reaction rate under acid-dependent and acid-independent conditions shows an initial retardation by acetic acid. The argument of ion-pair formation based on decrease of dielectric constant proposed to explain the kinetics in other aqueous solvent media was found useless to explain the behavior in acetic acid solutions. Other solvent parameters also did not provide satisfactory correlation with the kinetic results, thus, indicating the operation of more complex microscopic solute-solvent and solvent-solvent interactions. While solvent effects play some part in the rate process, the rate of reaction would tend to zero in the absence of H₂O and H⁺. This interesting observation proved useful in proposing a reaction mechanism that is consistent with the rate behavior over the entire range of solvent composition. The activity of water in the reaction medium is controlled by the content of acetic acid which can effect the structure of water through operation of hydrophobic forces and formation of hydrates. While acetic acid cannot possibly fulfill the role of water in occupying the vacated coordination position, the anomalous rise in rate even under some water deficient conditions seems to be related to the coordinating ability of HSO₄^? derived from H₂SO₄ present in the solution.     

Formation of diethylene glycol as a side reaction during production of polyethylene terephthalate

Polymers of poly(ethylene terephthalate) (PET) always contain a certain amount of incorporated diethylene glycol (DEG), substituting the incorporated glycol. DEG is formed in a side reaction during the ester interchange of dimethyl terephthalate (DMT) with ethylene glycol or during direct esterification of terephthalic acid with ethylene glycol, and to a smaller extent during the polycondensation of the low-molecular material. DEG is formed via an unusual type of reaction: ester + alcohol → ether + acid. Some evidence of this type of reaction is given by the formation of dioxane in low molecular PET and of methyl Cellosolve and methyl carbitol during the ester interchange of DMT with ethylene glycol and diethylene glycol, respectively. The strongest support for this type of reaction, however, was obtained from kinetic data. Polyesters of low molecular weight with OH group contents ranging from 3 to 0.5 mole/kg were heated at 270°C in sealed tubes for 1–7 hr. The kinetic equation for the proposed reaction is: d[DEG]/dt = k[OH] [ester]. With the aid of one rate constant the formation of DEG in all esters could be described.     

Brønsted酸性离子液体中的二甘醇脱水环化反应

首次报道了Brønsted酸性离子液体介质中的二甘醇的脱水环化反应,考察了不同的离子液体、离子液体/二甘醇摩尔比、反应温度和时间对反应的影响。结果表明,Brønsted酸性离子液体作为反应介质能够促进脱水环化反应的有效进行,且在离子液体1-(3-磺酸根丙基)-3-甲基咪唑硫酸氢盐([SPmim]HSO4)中,二甘醇的转化率和1,4-二氧六环的选择性更高。采用Hammett指示剂法测定了离子液体的酸度函数H0,其酸性强弱顺序为[SPmim]HSO4 > [Bmim]HSO4 > [Amim]HSO4 > [Hmim]BF4> [Bmim]H2PO4 >[Amim]H2PO4 > [Hmim]Tsa,这与离子液体在脱水环化反应中的催化效果一致。当温度为170 ˚C,离子液体/二甘醇摩尔比为1:1时,二甘醇在[SPmim]HSO4中反应2 h,转化率可达到97.0%,1,4-二氧六环的选择性为89.3%。     

A photocatalytic green system for chemoselective reduction of nitroarenes

A highly efficient photocatalytic reduction of nitroarenes using TiO₂/polyethylene glycol 400-water (TiO₂/PEG–H₂O) is reported. This system at deoxygenated and illuminated (sunlight or violet LED) conditions efficiently reduced nitroarenes using oxalic acid or ammonium formate as a sacrificial electron donor. Reducible functional groups such as chloro, hydroxy, flouro, bromo and carbonyl were intact under the optimized reaction conditions. The 0.1 and 0.5–1 mmol amount of nitroarenes was used under sunlight and violet LED (400 nm) irradiation, respectively. Reusability of the nanotitania was successfully carried out four times. The analyses of the recovered catalyst after five runs including TEM, XRD, TGA and CHN were done and results showed that PEG is located on TiO₂; no change in morphology, crystallinity and particle sizes was observed.     

A Study of the Activation of Carbon Using Sample Controlled Thermal Analysis

A constant rate method involving the control of the concentration of evolved CO₂ at a constant level was used to study the air activation of pure and copper-doped carbon prepared from sodium carboxymethylcellulose. Whereas under a linear heating regime, both types of carbon reacted suddenly and quickly with O₂, under constant rate conditions this violent reaction was avoided and oxidation proceeded steadily at a lower temperature until complete burn off of the carbon was achieved. The catalytic effect of the copper on carbon gasification was noted with lower reaction temperatures for both linear heating (380°C compared to 500°C) and for the constant rate experiments (320°C compared to 400°C). This revised version was published online in July 2006 with corrections to the Cover Date.     

Reactivity Tracers of the Hydrolysis of Fe(II)‐Bis(salicylidene) Complexes: Initial–Transition States Analysis and Enhanced Impact of Tensides on the Kinetic Trends

The kinetics of the acid hydrolysis reaction of Fe(II)‐bis(salicylidene) complexes were followed under pseudo–first‐order conditions ([H⁺] >> [complex]) at 298 K. The ligands of the studied azomethine complexes were derived from the condensation of salicylaldehyde with different five α‐amino acids. The hydrolysis reactions were studied in acidic medium at different ratios (v/v) of aqua–organic mixtures. The decrease in the dielectric constant values of the reaction mixture enhances the reactivity of the reaction. The transfer chemical potentials of the initial and transition states (IS–TS) from water into mixed solvents were determined from the solubility measurements combined with the kinetic data. Nonlinear plots of logk_obs versus 1/D (the reciprocal of the dielectric constant) suggest the influence of the solvation of IS–TS on the reaction reactivity. Furthermore, the acid hydrolysis reactions were screened in the presence of different concentrations of cationic and anionic tensides. The addition of surfactants to the reaction mixture accelerates the reaction reactivity. The obtained kinetic data were used to determine the values of δ_mΔG^# (the change in the activation barrier) for the studied complexes when transferred from “water to various ratios (v/v) of water–co‐organic binary mixtures” and from “water to water containing different [surfactant].” It was found that the reactivity of the acid hydrolysis reaction was controlled by the hydrophobicity of the studied chelates.     

Kinetics of polyesterification: Adipic acid with ethylene glycol, 1,4-butanediol,and 1,6-hexanediol

Polyesterifications of adipic acid with ethylene glycol, 1,4-butanediol, and 1,6-hexanediol in the absence and presence of the foreign acid (p-toluene sulfonic acid) as catalyst were carried out under constant reaction temperatures of 140–180°C (rather than at constant oil-bath temperatures) and at ratios of diol to diacid of 0.9867–3.5880. The experimental data fit the rate equations proposed by Chen and Wu: d(RCOOR′)/dt = k_ae^αp(RCOOH)²(R′OH) – k_h(H₂O)(RCOOR′) and d(RCOOR′)/dt = k_ac(AH)e^αp(RCOOH)(RO′H) – k_h(H₂O)(RCOOR′) for self-catalyzed and acid-catalyzed reactions, respectively; the data did not fit the other equations appearing in the literature. Here p is the conversion of acid, and α is the constant related to dielectric constants. The reaction rate constants and activation energies for self-catalyzed and acid-catalyzed reactions are calculated. The activation energy is found to decrease with chain length of the alkyl group of the diol. This result is consistent with that observed by Brauman and Blair using ion cyclotron resonance spectroscopy for the variation of acidity of alcohols with chain length of the alkyl group.