Synthesis of polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane via polysiloxane‐based macroinitiator in supercritical CO2

Polydimethylsiloxane‐block‐polystyrene‐block‐polydimethylsiloxane (PDMS‐b‐PS‐b‐PDMS) was synthesized by the radical polymerization of styrene using a polydimethylsiloxane‐based macroazoinitiator (PDMS MAI) in supercritical CO₂. PDMS MAI was synthesized by reacting hydroxy‐terminated PDMS and 4,4′‐azobis(4‐cyanopentanoyl chloride) (ACPC) having a thermodegradable azo‐linkage at room temperature. The polymerization of styrene initiated by PDMS MAI was investigated in a batch system using supercritical CO₂ as the reaction medium. PDMS MAI was found to behave as a polyazoinitiator for radical block copolymerization of styrene, but not as a surfactant. The response surface methodology was used to design the experiments. The parameters used were pressure, temperature, PDMS MAI concentration and reaction time. These parameters were investigated at three levels (?1, 0 and 1). The dependent variable was taken as the polymerization yield of styrene. PDMS MAI and PDMS‐b‐PS‐b‐PDMS copolymers obtained were characterized by proton nuclear magnetic resonance and infrared spectroscopy. The number‐ and weight‐average molecular weights of block copolymers were determined by gel permeation chromatography. Copyright © 2004 Society of Chemical Industry     

Conversion of carbohydrates into 5‐hydroxymethylfurfural in a green reaction system of CO2‐water‐isopropanol

In this work, a green reaction system of CO₂‐water‐isopropanol was developed for 5‐hydroxymethylfurfural (HMF) production. The conversion of fructose in a CO₂‐water system was first investigated, and the results showed this system could promote the formation of HMF compared to a pure water system. Then, isopropanol was introduced into the CO₂‐water system and the HMF formation became better because the solvent effect of isopropanol increased the tautomeric composition of fructofuranose, which was easy to form HMF. The existence of isopropanol was found to greatly suppress secondary reactions where HMF was converted to levulinic acid and insoluble humin. Meanwhile, the effects of reaction parameters on the conversion of fructose to HMF in the CO₂‐water‐isopropanol system were analyzed, and a high HMF yield of 67.14% was obtained. Finally, to further illustrate the merits of CO₂‐water‐isopropanol system, productions of HMF from other carbohydrates were tested and satisfactory yields were achieved. © 2016 American Institute of Chemical Engineers AIChE J, 63: 257–265, 2017     

Untersuchung der CO2‐Absorptionskinetik in wässrigen Lösungen von N,N‐Diethylethanolanmin und N‐Ethylethanolamin

N‐Ethylethanolamine (EEA) and N,N‐diethylethanolamine (DEEA) represent promising alkanolamines for CO₂ removal from gaseous streams, as they can be prepared from renewable resources. In this work, the reaction rate constant for the reaction between CO₂ and EEA and the liquid‐side mass transfer coefficient were determined from the absorption rate measurements in a blend comprising DEEA, EEA and H₂O. A stirred‐cell reactor was applied for the absorption studies, whereas a zwitterion mechanism for EEA and a base‐catalyzed hydration mechanism for DEEA were used to describe the reaction kinetics.     

Formic Acid: A Promising Bio‐Renewable Feedstock for Fine Chemicals

In light of the growing scarcity of petroleum‐based raw materials, carbon dioxide (CO₂) is becoming increasing attractive as organic carbon source. In this perspective, formic acid (HCOOH) might be an interesting bio‐renewable solution to store, transport, and activate carbon dioxide for the synthesis of value‐added chemicals. Herein, HCOOH has been successfully used as C₁ building block for the synthesis of a library of alcohols via a catalysed oxo‐synthesis, under green experimental conditions.     

Innovative Carbon Dioxide‐Capturing Organic Solvent: Reaction Mechanism and Kinetics

The reaction rates of CO₂ with an innovative CO₂‐capturing organic solvent (CO₂COS), consisting of blends of 2‐tert‐butyl‐1,1,3,3‐tetramethylguanidine (BTMG) and 1‐propanol, were obtained as function of BTMG concentration and temperature. A stopped‐flow apparatus with conductivity detection was used. The reaction was modeled by means of a modified termolecular reaction mechanism which resulted in a second‐order rate constant, and activation energies were calculated for a defined temperature range. Quantum chemical calculations at the B3LYP/6‐31G(d) level also produced the activation energy of this reaction system which strongly supports the experimental findings.     

One‐pot Synthesis of N‐Formyl‐O‐acyl‐ threo‐ and erythro‐DL‐β‐phenylserine Ethyl Esters and their Antiviral Properties

A series of N‐formyl‐O‐acyl‐β‐phenylserine derivatives 1b ‐ 7b were prepared by the interaction of N‐acyl‐b‐phenylserine ethyl esters 1a ‐ 7a with formic acid in presence of 1.5% HF. One‐pot acyl group N → O migration followed N‐formylation under elaborated reaction conditions. The kinetics of the reaction was investigated. The carboxylic acid moiety in the structure of β‐phenylserine had a strong influence on the reproduction of the used test‐viruses. The toxicity and antiviral activity is dependent on the diastereomeric forms of evaluated compounds.     

A Study on CO2 Absorption Kinetics by Aqueous Solutions of N,N‐Diethylethanolamine and N‐Ethylethanolamine

N‐Ethylethanolamine (EEA) and N,N‐diethylethanolamine (DEEA) represent promising candidate alkanolamines for CO₂ removal from gaseous streams, as they can be prepared from renewable resources. In this work, the reaction rate constant for the reaction between CO₂ and EEA was determined from the absorption rate measurements of CO₂ in a blend comprising DEEA, EEA and H₂O. A stirred‐cell reactor with a plane, horizontal gas‐liquid interface was used for the absorption studies. While the DEEA concentration in the formulated solution was varied in the range of 1.5–2.5 kmol/m³, the initial EEA concentration was 0.1 kmol/m³. A zwitterion mechanism for EEA and a base‐catalyzed hydration mechanism for DEEA were used to describe the reaction kinetics. At 303 K, the second‐order reaction rate constant for the CO₂ reaction with EEA was found to be 8041 m³/(kmol s). The liquid‐side mass transfer coefficient was also estimated, and its value (0.004 cm/s) is in line with those typical of stirred‐cell reactors.     

Influence of Solvent Polarity on the Mechanism and Efficiency of Formic Acid Reactive Extraction with Tri‐n‐Octylamine from Aqueous Solutions

The reactive extractions of formic acid with tri‐n‐octylamine (TOA) dissolved in three solvents with different dielectric constants (dichloromethane, butyl acetate, n‐heptane) without and with 1‐octanol as phase modifier were comparatively analyzed. The results indicated that the mechanism of the interfacial reaction between acid and extractant (Q) is controlled by the organic phase polarity. In the absence of 1‐octanol, the structures of the extracted complexes are (HA)₂Q₂ for dichloromethane and butyl acetate, and (HA)₂Q₄ for n‐heptane. These structures are modified by adding 1‐octanol and become (HA)₂Q for extraction in dichloromethane or butyl acetate, and (HA)₂Q₂ for extraction in n‐heptane. Although the presence of 1‐octanol improves the extraction efficiency, it leads to a reduction of the extraction constants for all considered solvents, an influence that is more significant for n‐heptane.     

Synthesis and properties of carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide) as a novel cellulose‐based superabsorbent

A new cellulose‐based superabsorbent polymer, carboxymethyl cellulose‐graft‐poly(acrylic acid‐co‐acrylamide), was prepared by the free‐radical grafting solution polymerization of acrylic acid (AA) and acrylamide (AM) monomers onto carboxymethyl cellulose (CMC) in the presence of N,N′‐methylenebisacrylamide as a crosslinker with a redox couple of potassium persulfate and sodium metabisulfite as an initiator. The influences of reaction variables such as the initiator content, crosslinker content, bath temperature, molar ratio of AA to AM, and weight ratio of the monomers to CMC on the water absorbency of the carboxymethylcellulose‐graft‐poly(acrylic acid‐co‐acrylamide) copolymer were investigated. The copolymer's structures were characterized with Fourier transform infrared spectroscopy. The optimum reaction conditions were obtained as follows: the bath temperature was 50°C; the molar ratio of AA to AM was 3 : 1; the mass ratio of the monomers to CMC was 4 : 1; and the weight percentages of the crosslinker and initiator with respect to the monomers were 0.75 and 1%, respectively. The maximum water absorbency of the optimized product was 920 g/g for distilled water and 85 g/g for a 0.9 wt % aqueous NaCl solution. In addition, the superabsorbent possessed good water retention and salt resistance. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1382–1388, 2007     

Synthesis of 2H‐Thiopyrans by Rhodium(II) Acetate‐Catalyzed Reaction of 4‐Amino‐2,5‐dihydro‐3‐thiophenecarbonitriles with α‐Diazocarbonyl Compounds. Part 1

4‐Amino‐2,5‐dihydro‐3‐thiophenecarbonitriles 1 reacted with dimethyl diazomalonate in the presence of rhodium(II) acetate to give regioselectively 4‐cyano‐2H‐thio‐pyrans 2 (C ₂— S insertion), and 5‐cyano‐2H‐thiopyrans (C ₅— S insertion) were not isolated. Similar insertion was also observed in the reaction of 1 with methyl diazoacetoacetate and ethyl diazobenzoylacetate. The starting compounds 1 were synthesized by the reaction of tetrahydro‐4‐oxo‐3‐thiophene‐carbonitrile with morpholine, piperidine, and pyrrolidine in the presence of formic acid in ethanol.     

Reaction kinetics of 2‐((2‐aminoethyl) amino) ethanol in aqueous and non‐aqueous solutions using the stopped‐flow technique

Observed pseudo‐first‐order rate constants (k_o) for the reaction between CO₂ and 2‐((2‐aminoethyl) amino) ethanol (AEEA) were measured using the stopped‐flow technique in an aqueous system at 298, 303, 308 and 313 K, and in non‐aqueous systems of methanol and ethanol at 293, 298, 303 and 308 K. Alkanolamine concentrations ranged from 9.93 to 80.29 mol m^?3 for the aqueous system, 29.99–88.3 mol m^?3 for methanol and 44.17–99.28 mol m^?3 for ethanol. Experimentally obtained rate constants were correlated with two mechanisms. For both the aqueous‐ and non‐aqueous‐AEEA systems, the zwitterion mechanism with a fast deprotonation step correlated the data well as assessed by the reported statistical analysis. As expected, the reaction rate of CO₂ in the aqueous‐AEEA system was found to be much faster than in methanol or ethanol. Compared to other promising amines and diamines studied using the stopped‐flow apparatus, the pseudo‐first‐order reaction rate constants were found to obey the following order: PZ (cyclic‐diamine) > EDA (diamine) > AEEA (diamine) > 3‐AP (primary amine) > MEA (primary amine) > EEA (primary amine) > MO (cyclic‐amine). The reaction rate constant of CO₂ in aqueous‐AEEA was double that in aqueous‐MEA, and the difference increased with an increase in concentration. All reaction orders were practically unity. With a higher capacity for carbon dioxide and a higher reaction rate, AEEA could have been a good substitute to MEA if not for its high thermal degradation. AEEA kinetic behaviour is still of interest as a degradation product of MEA. © 2012 Canadian Society for Chemical Engineering     

Benzothiazole‐accelerated sulfur vulcanization. I. 2‐Mercaptobenzothiazole as accelerator for 2,3‐dimethyl‐2‐butene

2,3‐Dimethyl‐2‐butene (TME) was used as a model compound for polyisoprene in a study of 2‐mercaptobenzothiazole (MBT)‐accelerated sulfur vulcanization. Mixes that contained curatives only were heated in a DSC to various temperatures, while those that also contained TME were heated isothermally at 150°C in evacuated, sealed glass ampules. Heated mixtures were analyzed for residual curatives, intermediates, and reaction products by HPLC. It is proposed that MBT forms polysulfidic species (BtS_xH) in the presence of sulfur and that these react with TME via a concerted, substitutive reaction pathway to form polysulfidic hydrogen‐terminated pendent groups of varying sulfur rank (TME–S_xH). MBT is released as a by‐product of this reaction. Crosslinking occurs slowly as a result of the interaction of polythiol pendent groups, the rate being dependent on the pendent group concentration. H₂S is released on crosslinking. 2,3‐Dimethyl‐2‐butene–1‐thiol was synthesized and reacted in the presence of sulfur to confirm the formation of crosslinked products (TME–S_x–TME). Benzothiazole‐terminated pendent groups (TME–S_xBt) were not observed. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1377–1385, 2000     

A kinetic model of nano‐CaO reactions with CO2 in a sorption complex catalyst

This article describes the reactive kinetics of nano‐CaO with CO₂ in a sorption complex catalyst. Based on an observation of nano‐CaO reaction with CO₂ has a fast surface reaction regime and followed by a slow diffusion‐controlled regime, a criterion has been proposed to divide the fast surface reaction regime and the slow diffusion‐controlled reaction regime. The kinetics of the fast surface reaction was studied, and a new ion reaction mechanism was proposed. A surface reaction‐controlled kinetic model with a Boltzmann equation, X = X_u?X_u/[1+exp((t?t₀)k/X_u)], was developed. Experiments using nano‐CaO to react with CO₂ in a fast surface reaction regime within a sorption complex catalyst were performed using thermogravimetric analysis at 773–873 K under a N₂ atmosphere with 0.010–0.020 MPa CO₂. The activation energy of the kinetic model for carbonation is 30.2 kJ/mol, and the average relative deviation of the sorption ratio is less than 9.8%. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Caged CO2 for the Direct Observation of CO2‐Consuming Reactions

CO₂‐consuming reactions, in particular carboxylations, play important roles in technical processes and in nature. Their kinetic behavior and the reaction mechanisms of carboxylating enzymes are difficult to study because CO₂ is inconvenient to handle as a gas, exists in equilibrium with bicarbonate in aqueous solution, and typically yields products that show no significant spectroscopic differences from the reactants in the UV/Vis range. Here we demonstrate the utility of 3‐nitrophenylacetic acid and related compounds (caged CO₂) in conjunction with infrared spectroscopy as widely applicable tools for the investigation of such reactions, permitting convenient measurement of the kinetics of CO₂ consumption. The use of isotopically labeled caged CO₂ provides a tool for the assignment of infrared absorption bands, thus aiding insight into reaction intermediates and mechanisms.     

Enzymatic Synthesis of 1‐Alkyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate Using a Novel Lysoplasmalogen‐Specific Phopholipase D

Many phospholipase Ds (PLDs) are known to catalyze transphosphatidylation as well as hydrolysis of phospholipids. Transphosphatidylation of lysoplasmalogen (LyPls)‐specific phospholipase D (LyPls‐PLD), which catalyzes hydrolysis of ether lysophospholipids such as LyPls and 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine (Lyso‐PAF), still remains unclear. This study aims to reveal the transphosphatidylation activity of LyPls‐PLD, that is, the production of cyclic ether lysophospholipid. The enzymatic reaction is conducted in a buffer system, and the reaction products of a novel LyPls‐PLD from Thermocrispum sp. are investigated using mass spectrometry (MS). MS analyses demonstrate the reaction products to consist of 100% 1‐hexadecyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate (cLyPA) and choline from Lyso‐PAF; however, 1‐alkenyl‐2‐hydroxy‐sn‐glycero‐2,3‐cyclic‐phosphate from 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphocholine and 1‐O‐1′‐(Z)‐octadecenyl‐2‐hydroxy‐sn‐glycero‐3‐phosphoethanolamine is not produced. These results are expected to help in elucidating the catalytic mechanism of LyPls‐PLD, that is, the rate‐limiting step, and indicate LyPls‐PLD to be useful for the one‐pot synthesis of cLyPA. Practical Applications: A novel phospholipase D, LyPls‐PLD, can exclusively synthesize cLyPA from Lyso‐PAF using a one‐step enzymatic reaction without an organic solvent. cLyPA could be expected to show bioactivities similar to those of cyclic phosphatidic acid, which promotes normal cell differentiation, hyaluronic acid synthesis, antiproliferative activity in fibroblasts, and inhibitory activity toward cancer cell invasion and metastasis.     

Preparation of Platinum‐Poly(O‐dihydroxybenzene) Composite Catalyst and Its Electrocatalytic Activity Toward Methanol and Formic Acid Oxidation

A composite catalyst has been successfully prepared by dispersing Pt nanoparticles on a poly(o‐dihydroxybenzene) (PoDHB) modified glassy carbon (GC) electrode and characterized by SEM, EDX, and electrochemical analysis. Compared with Pt nanoparticles deposited on the bare GC, the Pt/PoDHB/GC exhibits higher catalytic activity and stronger poisoning tolerance for electro‐oxidation of methanol and formic acid. The enhanced performance could be attributed to the increase of electrochemical active surface area (EASA) arisen from the PoDHB modification. Furthermore, performance limiting factors such as platinum loading, polymer mass, H₂SO₄, methanol, and formic acid concentrations have been evaluated for optimizing the electrocatalytic activities.     

Stability constants of polymer‐bound iminodiacetate‐type chelating agents with some transition‐metal ions

A chelating vinyl monomer, glycidyl methacrylate (GMA)–iminodiacetic acid (IDA), was formed by the reaction between GMA and IDA. Three polymeric chelating agents, PGMA–IDA, PGMA–IDA‐co‐methyl acrylate (MA), and PGMA–IDA‐co‐acrylamide (AAm), were also synthesized. Acid dissociation constants and stability constants of these chelating agents with Ni(II), Zn(II), and Co(II) were determined by means of potentiometric titration and ultraviolet–visible spectrophotometry, respectively. The values of K_a1 and K_a2 of all the polymeric chelating agents were smaller than those of GMA–IDA. The stability constants of all the polymeric chelating agents were larger than those of GMA–IDA. Increasing the MA content within PGMA–IDA‐co‐MA affected the stability constant only slightly. A proper molar ratio of AAm in PGMA–IDA‐co‐AAm, stability constants was 30–60 times greater than that of GMA–IDA. However, as the molar content of AAm increased, the stability constant of PGMA–IDA‐co‐AAm decreased. The results obtained in the polymer system are explained in terms of the polymer's stereo and entanglement structure, the neighboring effect, and the hydrophobic/hydrophilic nature of MA or AAm. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 1986–1994, 2002     

Synthesis and characterization of novel core‐shell magnetic nanogels based on 2‐acrylamido‐2‐methylpropane sulfonic acid in aqueous media

Ultrafine well‐dispersed Fe₃O₄ magnetic nanoparticles were directly prepared in aqueous solution using controlled coprecipitation method. The synthesis of Fe₃O₄/poly (2‐acrylamido‐2‐methylpropane sulfonic acid) (PAMPS), Fe₃O₄/poly (acrylamide‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AM‐co‐AMPS) and Fe₃O₄/poly (acrylic acid‐co‐2‐acrylamido‐2‐methylpropane sulfonic acid) poly(AA‐co‐AMPS) ‐core/shell nanogels are reported. The nanogels were prepared via crosslinking copolymerization of 2‐acrylamido‐2‐methylpropane sulfonic acid, acrylamide and acrylic acid monomers in the presence of Fe₃O₄ nanoparticles, N,N′‐methylenebisacrylamide (MBA) as a crosslinker, N,N,N′,N′‐tetramethylethylenediamine (TEMED) and potassium peroxydisulfate (KPS) as redox initiator system. The results of FTIR and ¹H‐NMR spectra indicated that the compositions of the prepared nanogels are consistent with the designed structure. X‐ray powder diffraction (XRD) and transmission electron microscope (TEM) measurements were used to determine the size of both magnetite and stabilized polymer coated magnetite nanoparticles. The data showed that the mean particle size of synthesized magnetite (Fe₃O₄) nanoparticles was about 10 nm. The diameter of the stabilized polymer coated Fe₃O₄ nanogels ranged from 50 to 250 nm based on polymer type. TEM micrographs proved that nanogels possess the spherical morphology before and after swelling. These nanogels exhibited pH‐induced phase transition due to protonation of AMPS copolymer chains. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Modeling of CO2‐Hydrate Formation at the Gas‐Water Interface in Sand Sediment

Sub‐seabed geological storage of CO₂ in the form of gas hydrate is attractive because clathrate hydrate stably exists at low temperature and high pressure, even if a fault occurs by diastrophism like a big earthquake. For the effective design of the storage system it is necessary to model the formation of CO₂‐hydrate. Here, it is assumed that the formation of gas hydrate on the interface between gas and water consists of two stages: gas diffusion through the CO₂‐hydrate film and consequent CO₂‐hydrate formation on the interface, between film and water. Also proposed is the presence of a fresh reaction interface, which is part of the interface between the gas and aqueous phases and not covered with CO₂‐hydrate. Parameters necessary to model the hydrate formation in sand sediment are derived by comparing the results of the present numerical simulations and the measurements in the literature.     

Determination of kinetics of CO2 absorption in solutions of 2‐amino‐2‐methyl‐1‐propanol using a microfluidic technique

The kinetics for the reactions of carbon dioxide with 2‐amine‐2‐methyl‐1‐propanol (AMP) and carbon dioxide (CO₂) in both aqueous and nonaqueous solutions were measured using a microfluidic method at a temperature range of 298–318 K. The mixtures of AMP‐water and AMP‐ethylene glycol were applied for the working systems. Gas‐liquid bubbly microflows were formed through a microsieve device and used to determine the reaction characteristics by online observation of the volume change of microbubbles at the initial flow stage. In this condition, a mathematical model according to zwitterion mechanism has been developed to predict the reaction kinetics. The predicted kinetics of CO₂ absorption in the AMP aqueous solution verified the reliability of the method by comparing with literatures’ results. Furthermore, the reaction rate parameters for the reaction of CO₂ with AMP in both solutions were determined. © 2015 American Institute of Chemical Engineers AIChE J, 61: 4358–4366, 2015