Effect of the structure of commercial poly(ethylene oxide-b-propylene oxide) demulsifier bases on the demulsification of water-in-crude oil emulsions: elucidation of the demulsification mechanism

Water-in-crude oil emulsions are formed during petroleum production and asphaltenes play an important role in their stabilization. Demulsifiers are added to destabilize such emulsions,however the demulsification mechanism is not completely known. In this paper, the performances of commercial poly(ethylene oxide-b-propylene oxide) demulsifiers were studied using synthetic water-in-oil emulsions and model-systems (asphaltenes in organic solvent). No change in the asphaltene aggregate size induced by the demulsifier was observed. The demulsification performance decreased as the asphaltene aggregate size increased, so it can be suggested that the demulsification mechanism is correlated to the voids between the aggregates adsorbed on the water droplets surface.

Poly(ethylene-co-methyl acrylate)/poly(caprolactone) triol blends for drug delivery systems: characterization and drug release

Poly(ethylene-co-methyl acrylate) (EMA) and poly (caprolactone) triol (PCL-T) blends, a biodegradable aliphatic polyester with low molecular weight and moderate water solubility containing diltiazem hydrochloride (DZ) were studied in terms of the thermal and morphological properties, and drug release mechanism. An increase in the PCL-T content in the EMA/PCL-T/DZ films decreased the degree of DZ crystallinity. Drug release from these films is temperature-dependent, and it is possible to modify the drug release rate by adjusting the EMA/PCL-T composition of the blends. The mechanism of drug release is governed by PCL-T melting and PCL-T leaching from EMA matrix.

Synthesis and NMR characterization of aliphatic-aromatic copolyesters by reaction of poly(ethylene terephthalate) post-consumer and poly(ethylene adipate)

An aliphatic-aromatic copolyester of poly(ethylene terephthalate), PET, and poly(ethylene adipate), PEA, PET-co-PEA, was synthesized by the high temperature melt reaction of post-consumer PET and PEA. As observed by NMR spectroscopy, the reaction yielded random copolyesters in a few minutes through ester-interchange reactions, even without added catalyst. The copolyesters obtained in the presence of a catalyst presented higher intrinsic viscosity than that obtained without the addition of catalyst, due to simultaneous polycondensation and ester-interchange reactions. The structure of the aliphatic-aromatic copolyesters obtained in different PET/PEA ratio is random as observed by NMR analysis.

Discrepancies over the onset of surfactant monomer aggregation interpreted by fluorescence, conductivity and surface tension methods

Molecular probe techniques have made important contributions to the determination of microstructure of surfactant assemblies such as size, stability, micropolarity and conformation. Conductivity and surface tension were used to determine the critical aggregation concentration (cac) of polymer-surfactant complexes and the critical micellar concentration (cmc) of aqueous micellar aggregates. The results are compared with those of fluorescent techniques. Several surfactant systems were examined, 1-butanol-sodium dodecylsulfate (SDS) mixtures, solutions containing poly(ethylene oxide)-SDS, poly(vinylpyrrolidone)-SDS and poly(acrylic acid)-alkyltrimethylammonium bromide complexes. We found differences between the cac and cmc values obtained by conductivity or surface tension and those obtained by techniques which use hydrophobic probe.

Síntese e caracterização dos nanocompósitos K0,1(PEO)xMoS2 (X= 0,5; 1,2)

The reaction of an aqueous solution of poly(ethylene oxide) (peo - mw 100.000) with a neutral aqueous suspension of single layers of MoS2 was studied. The single layers aqueous suspension was prepared by first intercalating lithium (using n-Butyllithium in n-hexane) and reaction of these ternary compound with water under ultrasound stirring. The suspension was washed several times with water until neutral pH. The suspension was mixed with the PEO aqueous solution in the presence of KCl. Two single phase compounds were obtained with the expansion of 4,8 and 9,0Å, attributed to the solvation of the intercalated potassium cations with mono and double layers, respectively.

Interação tensoativo/hidrótropo em sistemas aquosos, utilizando ressonância magnética nuclear de ¹H e 13C

In this work, it was studied the behavior of the nonionic surfactant aqueous solutions, containing or not a hydrotropic agent, by resonance magnetic nuclear (NMR). We have studied monofunctional diblock copolymers of poly(propylene oxide-ethylene oxide) (R-PPO-PEO-OH, where R length is linear C4) as nonionic surfactant and sodium p-toluenesulfonate (NaPTS) as hydrotropic agent. The critical micelle concentration (CMC) of the aqueous copolymer solution was obtained from ¹H-NMR. The preliminary study of the interaction between the copolymer, under the unimer and micelle forms, and the hydrotrope, in aqueous solutions, was evaluated by ¹H-NMR and 13C-NMR.

Efeito do polietilenoglicol e da albumina na imobilização de lipase microbiana e na catálise em meio orgânico

Poly (ethylene) glycol (PEG) and bovine serum albumin (BSA), as additive agents, were used to enhance the activity of immobilized microbial lipase in organic solvent. Controlled pore silica (CPS) was selected as matrix and different immobilization procedures were evaluated: directly lipase binding on CPS and simultaneous addition of lipase and additive agent on the same support. The highest coupling yield (59.6%) was attained when the immobilization procedure was performed at lipase loading of 150 U/g support in the presence of PEG-1.500. This immobilized system was used in esterification reactions under repeated batch cycles and the biocatalyst half-life was found to increase 2.7 times when compared with the control.

Produção de etilenoglicóis e derivados por reações catalíticas do óxido de eteno

Products resulting from the ethoxylation of hydroxylated compounds, especially water and ethanol, are of great commercial importance. This work presents several aspects concerning the catalytic reactions of ethylene oxide, a chemical substance used in the production of a wide variety of products. Mechanisms of ethoxylation, distribution of products, formation of undesired by-products and perspectives for new processes using heterogeneous catalysis are also reviewed and discussed.

Influence of the temperature and type of salt on the phase equilibrium of peg 1500 + potassium phosphate and peg 1500 + sodium citrate aqueous two-phase systems

The present work analyzed the effect of the temperature and type of salt on the phase equilibrium of aqueous two-phase systems (ATPS) formed by poly (ethylene glycol) (PEG) 1500 + potassium phosphate, from (278.15 to 318.15) K, and PEG 1500 + sodium citrate, from (278.15 to 298.15) K. The rise of the temperature normally increased the slope of the tie line (STL). With respect to the influence of the type of salt, sodium citrate showed better capability to induce phase separation, when compared to potassium phosphate.

Síntese e caracterização de dispersões aquosas de poliuretanos à base de copolímeros em bloco de poli(glicol etilênico) e poli(glicol propilênico)

Non-polluting polyurethane aqueous dispersions, with 40% of solids content, were synthesized based on block copolymers of poly(ethylene glycol) and poly(propylene glycol) (PEG-b-PPG), with PEG hydrophilic segments content of 7 and 25%, poly(propylene glycol) (PPG), dimethylolpropionic acid (DMPA), isophorone diisocyanate (IPDI), and hydrazine. Different formulations were synthesized by varying the equivalent-grams ratios between isocyanate and hydroxyl groups (NCO/OH) and PPG and (PEG-b-PPG). The presence of high amounts of PEG in the formulations provoked the formation of gels. Average particle size and viscosity of the dispersions were determined. Mechanical properties and water absorption resistance of cast films were evaluated.

Medidas de tensão superficial pelo método de contagem de gotas: descrição do método e experimentos com tensoativos não-iônicos etoxilados

Surface tension knowledge of surfactants aqueous solutions is important during amphiphilic molecule manufacturing and new product development, as feedback information to handle synthesis parameters to target performance. Drop counting method is an interesting simplification of drop weight method for surface tension measurements. A simple laboratory measurement device, with capability for temperature control, was assembled to allow investigation of ethoxylated surfactants. The implementation of the method was preceded by a detailed investigation of two factors that may affect the measured surface tension: drop formation velocity and surfactant ethoxylation degree. The limitations of the method are discussed on this basis.

A INFLUÊNCIA DA LIGAÇÃO DE HIDROGÊNIO EM REAÇÕES QUÍMICAS: REAÇÃO DE PRILESCHAJEW

Theoretical analysis at the BHandHLYP/6-311++G(d,p) level of theory with the support of QTAIM calculations was used to reinvestigate the structure of an intermolecular system formed between ethylene oxide (C2H4O) and formic acid (HCO2H) after the epoxidation known as the Prileschajew reaction. Geometric and infrared vibration results revealed that HO2CH forms a strong hydrogen bond with C2H4O followed by a larger red-shift of the H−O bond. NBO analysis was applied to justify this frequency shift. Finally, QTAIM calculations identified the formation of two hydrogen bonds, namely O···H−O and H···O=C.

DEGRADAÇÃO MICROBIOLÓGICA E ENZIMÁTICA DE POLÍMEROS: UMA REVISÃO

Polymer recycling has been one of the most important trend in the petrochemical area. Among different technologies, biotechnological (enzymatic and/or microbial) degradation of polymers for the recovery of monomers and oligomers is environmentally-friendly and meet some green chemistry principles. In this work, conditions for the biotechnological degradation of some industrially-relevant polymers (e.g. poly(ethylene terephthalate) and polyethylene) were revised, and the main biocatalysts were identified. In most cases, biodegradation mechanisms are still unclear, thus being necessary more studies to unravel these promising bioprocesses. Polymer biodegradation studies also present considerable importance for other fields, including biomedical and agricultural.

Use of blends of bioabsorbable poly(L-lactic acid)/poly(hydroxybutyrate- co-hydroxyvalerate) as surfaces for Vero cell culture

Vero cells, a cell line established from the kidney of the African green monkey (Cercopithecus aethiops), were cultured in F-10 Ham medium supplemented with 10% fetal calf serum at 37°C on membranes of poly(L-lactic acid) (PLLA), poly(hydroxybutyrate-co-hydroxyvalerate) (PHBV) and their blends in different proportions (100/0, 60/40, 50/50, 40/60, and 0/100). The present study evaluated morphology of cells grown on different polymeric substrates after 24 h of culture by scanning electron microscopy. Cell adhesion was also analyzed after 2 h of inoculation. For cell growth evaluation, the cells were maintained in culture for 48, 120, 240, and 360 h. For cytochemical study, the cells were cultured for 120 or 240 h, fixed, processed for histological analysis, and stained with Toluidine blue, pH 4.0, and Xylidine ponceau, pH 2.5. Our results showed that cell adhesion was better when 60/40 and 50/50 blends were used although cells were able to grow and proliferate on all blends tested. When using PLLA/PHBV (50/50) slightly flattened cells were observed on porous and smooth areas. PLLA/PHBV (40/60) blends presented flattened cells on smooth areas. PLLA/PHBV (0/100), which presented no pores, also supported spreading cells interconnected by thin filaments. Histological sections showed that cells grew as a confluent monolayer on different substrates. Cytochemical analysis showed basophilic cells, indicating a large amount of RNA and proteins. Hence, we detected changes in cell morphology induced by alterations in blend proportions. This suggests that the cells changed their differentiation pattern when on various PLLA/PHBV blend surfaces.

Phase transitions in biodegradable films based on blends of gelatin and poly (vinyl alcohol)

The aim of this work was to study the effect of the hydrolysis degree (HD) and the concentration (C PVA) of two types of poly (vinyl alcohol) (PVA) and the effect of the type and the concentration of plasticizers on the phase properties of biodegradable films based on blends of gelatin and PVA, using a response-surface methodology. The films were made by casting and the studied properties were their glass (Tg) and melting (Tm) transition temperatures, which were determined by diferential scanning calorimetry (DSC). For the data obtained on the first scan, the fitting of the linear model was statistically significant and predictive only for the second melting temperature. In this case, the most important effect on the second Tm of the first scan was due to the HD of the PVA. In relation to the second scan, the linear model could be fit to Tg data with only two statistically significant parameters. Both the PVA and plasticizer concentrations had an important effect on Tg. Concerning the second Tm of the second scan, the linear model was fit to data with two statistically significant parameters, namely the HD and the plasticizer concentration. But, the most important effect was provoked by the HD of the PVA.