Nonionic Polymeric Surfactants Research Articles

A dendritic-linear block copolymer as a thermoresponsive non-ionic polymer surfactant

Issues related to water pollution by a variety of pollutants must be resolved for sustainable development. Over the past decades, several methods have been developed for pollutant removal from aqueous media. In this study, a dendritic-linear block copolymer (Den-PEtOx) was synthesized as a thermoresponsive non-ionic polymer surfactant, and its structure was confirmed by NMR, MALDI-TOF-MS, and SEC measurements. Den-PEtOx formed micelle structures with an average diameter of 121.6 nm and effectively encapsulated Rose Bengal (RB) red dye dissolved in aqueous media. RB-encapsulated Den-PEtOx exhibited a phase transition temperature at 62.4 °C owing to its thermoresponsive poly(2-ethyl-2-oxazoline) segment. Greater than 99% of RB in the aqueous media was successfully removed with Den-PEtOx via filtration above the phase transition temperature.

Evaluation of the biological activity of the prepared nonionic polymeric based on the acrylated polyethylene glycol

Nonionic polymeric surfactants were prepared by acrylated of poly (ethylene glycol) (PEG) esterfied with oleic or palmitic acid. The unique structural features of these polymeric surfactants were investigated by using Fourier transformer infrared spectroscopy (FTIR) and X-ray diffraction (XRD). The surface tension at different temperatures of these compounds was investigated. The surface parameters including critical micelle concentration (CMC), maximum surface excess (Γmax), minimum surface area (Amin), efficiency (Pc20) and effectiveness (πCMC) were studied and calculated. The biological activity of these prepared compounds was evaluated and determined via the inhibition zone diameter against different microorganisms. From the outcomes, it was noticed that these compounds possess superior surface properties and perfect antimicrobial action.

Dehydroabietyl Glycidyl Ether Grafted Hydroxyethyl Chitosan: Synthesis, Characterization and Physicochemical Properties

AbstractA series of novel polymeric nonionic surfactants based on water-soluble N,O-hydroxyethyl chitosan (N,O-HECTS) and dehydroabietyl glycidyl ether (DAGE), DAGE-g-N,O-HECTSs, were synthesized by an additive reaction between N,O-HECTS and DAGE. The structures of DAGE-g-N,O-HECTSs were characterized by FT-IR and 1H NMR. The substitution degree of hydroxyethylation (DSHE) of N,O-HECTS and the grafting degree (DG) of DAGE onto N,O-HECTS for DAGE-g-N,O-HECTSs were determined by elemental analysis. The surface activities of DAGE-g-N,O-HECTSs in aqueous solution were investigated by measuring the surface tension. The experimental results showed that the degree of grafting (DG) of DAGE-gN,O-HECTSs could have a significant impact on their critical micelle concentrations (CMCs) and surface tensions at the CMC (γCMC), but the DG of DAGE-g-N,O-HECTSs had almost no effect on the minimum of surface tensions (γmin). When using the DAGE-g-N,O-HECTSs as emulsifier, the increase in DG had a favorable influence on the stability of an emulsion of water and benzene. At a DG greater than 40.45%, the emulsifying power of DAGE-g-N,O-HECTS exceeded that of Tween-60.

Novel Star Polymeric Nonionic Surfactants as Crude Oil Emulsion Breakers

AbstractThe principle focus of this work is to address the issues associated with the existence of water in crude oil, especially corrosion, scaling, viscosity, and catalyst suppression problems. This work aims to prepare star polymer nonionic surfactants based on (2Z,2′Z,2″Z)‐4,4′,4″‐((nitrilotris(ethane‐2,1‐diyl))tris(oxy))tris(4‐oxobut‐2‐enoic acid) to be used as demulsifiers. To achieve this aim, maleic anhydride was reacted with triethanolamine followed by esterification with the polyethylene oxide polypropylene oxide copolymer (PPO‐PEO 5000) and silicone polyether (ABIL B 8843). The chemical structure of the prepared compounds was assessed using gel permeation chromatography (GPC), Fourier transform infrared (FT‐IR), and 1H NMR. Demulsifier performance was determined by quantifying surface tension (ST), dynamic interfacial tension and interfacial rheology, partition coefficient (PC), and relative solubility number (RSN). The efficacy of the prepared emulsion breakers on asphaltenic crude oil emulsion was examined using the bottle test. The research results demonstrated that the prepared breaker based on the silicone polymer was more efficient in breaking the asphaltenic crude oil emulsion than a block copolymer and EO/PO‐based copolymers at 1500 ppm and after 120 min.

Oxidation-responsive polyether block copolymers lead to non-ionic polymer surfactants with multiple amine N-oxides

Oxidation of tertiary amines leads to multiple amine N-oxide moieties and a highly polar polyether structure. Combination with the apolar poly(propylene oxide) affords unusual surfactants.

RESEARCH OF ENVIRONMENTALLY CLEAN TECHNICAL DETERGENTS

Problematic places in the modern economy is reckless depletion of natural resources, raw materials and fuels, excessive using of energy and environmental issues. Solving these issues in the gas and chemical industry achieved by preventing formation of the deposits on the compressor’s elements, and also implementation of the non-waste and low-waste productions and alternative energy sources. The deposits on the internal elements of the gas-air channels results in a significant loss of power, increases energy costs, reduces operational reliability of plants, through the activation of corrosion and erosion. So actual is development of technical detergents based on environmentally friendly surfactants and inorganic ingredients that do not contain deficit fire dangerous light oils, and also have high washing ability and low corrosion activity. Effective and non-phosphatic ecologically safe technical detergents (TD) based on polymeric non-ionic surfactants have been developed, as the composite surfactant of multifunctional action CF-10 is considered. The interaction of nonionic surfactants with the ingredients of the contamination of gas turbine aggregates was studied by various physicochemical methods (spectrophotometry, IR spectroscopy, electron paramagnetic resonance, electro-chemical polarization resistance method). Bibl. 10, Fig. 4.

A review of shampoo surfactant technology: consumer benefits, raw materials and recent developments.

Surfactants form the core of all shampoo formulations, and contribute to a wide range of different benefits, including cleansing, foaming, rheology control, skin mildness and the deposition of benefit agents to the hair and scalp. The purpose of this review was to assist the design of effective, modern, shampoo surfactant technologies. The mechanisms through which surfactants help deliver their effects are presented, along with the appraisal techniques through which surfactant options can be tested and screened for product development. The steps that should be taken to select the most appropriate blend of surfactants are described, and useful information on the most widely used surfactants is provided. The review concludes with an examination of recent developments in 'greener' surfactants, 'sulphate-free' technologies and structured liquid phases for novel sensory properties and for suspending benefit agents.

Efficient nano-filler for the phase transformation in polyvinylidene fluoride nanocomposites by using nanoparticles of stannous sulfate

Nanocomposites of PVDF-tin sulphate were synthesized by solution-mixing technique with 0–4% w/w loadings of SnSO4 nanoparticles. The novel nanoparticles of SnSO4 were synthesized via in situ deposition method and its surface modification was performed by nonionic polymeric surfactant PEG. XRD analysis revealed that the average diameter of synthesized nanoparticles was 45 nm. Polymeric films of PVDF/SnSO4 nanocomposites were characterized by FTIR, SEM, EDS, TG/DTA, DSC and UV–vis spectrum. FTIR absorption bands show that α and β-phases coexist in pure PVDF which was supported by the 2θ value of XRD at 20.75°. This critical data shows that the phase of PVDF was completely transformed from α to β with incorporation of SnSO4 nanoparticles. The UV absorbance intensity was increased, Tg and Td were decreased with the increase in nanoparticles loadings in polymer matrix. The prepared nanocomposites could be used as a smart material for sensing device.

Development of microemulsions to reduce the viscocity of crude oil emulsions

The formation of water-in-oil (W/O) emulsions during extraction of petroleum is a major problem, because these emulsions increase the oil’s viscosity and thus significantly lower the production rates. In these situations, chemical products called emulsion viscosity reducers (EVRs) can be injected during crude oil production. The development of EVRs consisting of oil-in-water (O/W) microemulsions can attract a good deal of attention due to the possibility of reducing costs and increasing environmental friendliness (they are mostly composed of water instead of large volumes of organic solvents). This article describes the preparation of O/W microemulsions, using the solvents kerosene, Solbrax or xylene as components of the oil phase and three commercial nonionic polymer surfactants based on poly(ethylene oxide) as the aqueous phase. For this purpose, first ternary phase diagrams (water/oil/surfactant) were constructed to determine the optimal concentrations of these components to prepare the O/W microemulsions, selecting 16wt% surfactant, 4wt% oil phase and 80wt% aqueous phase as the common composition of all the systems studied. The efficiency of the microemulsion systems was investigated by rheological tests in synthetic water/oil emulsions prepared from a heavy crude oil (°API 20). The microemulsion systems were tested regarding their interfacial activity by analyzing the interfacial tension and the average size of the water droplets dispersed in the crude oil, before and after adding the systems developed. The results showed that the performance of the O/W microemulsions did not depend on the type of oil phase, but that the insertion of an oil phase (i.e., the formation of an O/W microemulsion) improved the performance of the surfactant in the medium compared to the efficiency of the aqueous surfactant solutions.

Steady-shear rheology and activation thermodynamics of the interpolymer complex between nonionic polymeric surfactant and hydrophobically modified polyacrylic acid in propylene glycol–water mixture

Rheology of the individual polymer solutions and complex polymer mixtures was studied in the temperature range from 30 to −20 °C. Based on the obtained data steady-shear flow properties and thermodynamic parameters of a viscous flow were calculated. Exploiting the flow parameters such as the flow behavior index it was demonstrated that addition of synthesized anionic polymeric surfactant—polyvinyl octanal (PVO) to the polyelectrolyte solution enhanced pseudoplasticity of the obtained liquids at low temperatures. Along with that, the anomalous behavior of the activation enthalpy and activation entropy as a function of temperature was observed for the polyelectrolyte solutions containing PVO. Thus, it was shown that relatively high initial values of ΔH A diminish sharply with an increase in temperature and TΔS A values decrease dramatically below 0 °C. The obtained results were in line with the concept of the critical temperature observed for the strongly associated polymeric systems in water–glycol mixtures. In the light of the findings it was assumed that specific interpolymer association occurs at low temperatures resulting in consequent increase in the values of apparent viscosity and pseudoplasticity of the studied polymeric liquids. It was also suggested that studied system is well suited for the formulation of the thickened aircraft deicing fluids.

Effect of nanoclay and barium sulfate nanoparticles on the thermal and morphological properties of polyvinylidene fluoride nanocomposites

The thermal, morphological and optical studies of BaSO4 and MMT (nanoclay) embedded in PVDF were investigated. Nanocomposites samples of PVDF–BaSO4–MMT were prepared by varying the loadings (1–4 mass%) in case of BaSO4 and MMT nanomaterials, respectively. Polyvinylidene fluoride–barium sulfate-montmorillonite (PVDF–BaSO4–MMT) nanocomposites were prepared by solvent-mixing technique. Nanoparticles were synthesized by in situ deposition technique with the help of nonionic polymeric surfactant, and the particle size of nanoparticles was recognized by scanning electron microscopy (SEM) analysis which confirms that the particle has diameter of 80–90 nm. As prepared, nanocomposites films (thickness, 25 μm) were characterized by Fourier transform infrared microscopy (FTIR), SEM and electron diffraction spectroscopy (EDS). FTIR shows that all the chemical constituents were present in the nanocomposites, whereas SEM analysis suggested that the nanofillers dispersed well in polymer matrix and EDS showed the elemental composition of nanocomposite samples. Thermal properties of nanocomposites were studied by using TG/DTA/DTG. TG/DTA studies showed decomposition temperature of pure PVDF is 473.5 °C. The decomposition temperature (Td) of nanocomposites was increased by 93 °C in case of nanocomposites with addition of both BaSO4 and MMT nanomaterials. The difference in the thermal degradation temperature was found to be 1.2% higher in case of addition of BaSO4 nanoparticle as compared to nanoclay. The obtained transparent nanocomposite films were characterized by using UV–Vis spectrophotometer which shows that transparencies of nanocomposites are maintained in visible region, the intensity of absorption band in UV region is increased with the addition of BaSO4 nanoparticles, while in case of addition of nanoclay the UV region does not show drastic changes. Addition of both nanoparticle and nanoclay shows higher absorption in comparison with the individual samples. But further, doubling the amount of nanoparticle and nanoclay shows decrease in UV absorption. Overall, the results of thermal studies show that the incorporation of BaSO4 and MMT could significantly improve the thermal properties of nanocomposites.

Synthesis of nonionic polymeric surfactants with amide oxime terminal groups

Synthesis of nonionic polymeric surfactants with amide oxime terminal groups

Thermodynamics of aggregate formation between a non-ionic polymer and ionic surfactants: An isothermal titration calorimetric study

This report examines the energetics of aggregate formation between hydroxypropyl methylcellulose (HPMC) and model ionic surfactants including sodium dodecyl sulfate (SDS) at pharmaceutically relevant concentrations using the isothermal titration calorimetry (ITC) technique and a novel treatment of calorimetric data that accounts for the various species formed. The influence of molecular weight of HPMC, temperature and ionic strength of solution on the aggregate formation process was explored. The interaction between SDS and HPMC was determined to be an endothermic process and initiated at a critical aggregation concentration (CAC). The SDS-HPMC interactions were observed to be cooperative in nature and dependent on temperature and ionic strength of the solution. Molecular weight of HPMC significantly shifted the interaction parameters between HPMC and SDS such that at the highest molecular weight (HPMC K–100M;>240kDa), although the general shape of the titration curve (enthalpogram) was observed to remain similar, the critical concentration parameters (CAC, polymer saturation concentration (Csat) and critical micelle concentration (CMC)) were significantly altered and shifted to lower concentrations of SDS. Ionic strength was also observed to influence the critical concentration parameters for the SDS-HPMC aggregation and decreased to lower SDS concentrations with increasing ionic strength for both anionic and cationic surfactant-HPMC systems. From these data, other thermodynamic parameters of aggregation such as ΔHagg°, ΔGagg°, Hagg°, ΔSagg°, and ΔCp were calculated and utilized to postulate the hydrophobic nature of SDS-HPMC aggregate formation. The type of ionic surfactant head group (anionic vs. cationic i.e., dodecyltrimethylammonium bromide (DTAB)) was found to influence the strength of HPMC-surfactant interactions wherein a distinct CAC signifying the strength of HPMC-DTAB interactions was not observed. The interpretation of the microcalorimetric data at different temperatures and ionic strengths while varying properties of polymer and surfactant was a very effective tool in investigating the nature and energetics of HPMC and ionic surfactant interactions.

Colloidal behavior of detonation nanodiamonds in the aqueous-organic liquid systems in the presence of pluronic P123

Polymeric nonionic surfactant pluronic P123 significantly increases the distribution ratio of nanodiamonds in the aqueous-organic liquid systems.

Formation of multi-compartmental particles by controlled aggregation of liposomes

The formation of multi-compartmental colloidal particles by controlled aggregation of 100nm cationic liposomes was investigated. The aggregation was performed under quiescent (perikinetic) conditions and was controlled by the ionic strength of the solution. The time required for obtaining 500nm particles by liposome aggregation ranged from several hours to a few minutes when increasing the NaCl concentration from 50mM to 100mM. It was shown that the aggregation process can be effectively terminated by capping the liposome clusters by a biocompatible non-ionic polymeric surfactant (Poloxamer 188). The clusters were stable in time and resistant to further increase in ionic strength as well as to mechanical agitation. These results demonstrate that multi-compartmental liposome-based carriers with a controlled size can be prepared in a relatively simple and robust way, and used for further studies in environments with variable salinity and hydrodynamic conditions.

The effects of non-ionic polymeric surfactants on the cleaning of biofouled hydrogel materials

Block co-polymer surfactants have been used for cleaning hydrogel medical devices that contact the body (eg contact lenses) because of their biocompatibility. This work examined the relationship between concentration and detergency of two non-ionic polymeric surfactants (Pluronic F127 and Triton X-100) for cleaning protein soil, with anionic surfactants (sodium dodecyl sulfate and sodium laureth sulfate) as positive controls. Surface plasmon resonance was used to quantify removal of simulated tear soil from self-assembled monolayer surfaces, and a microplate format was used to study the removal of fluorescently labeled soil proteins from contact lenses. While detergency increased as a function of concentration for anionic surfactants, it decreased with concentration for the two polymeric surfactants. The fact that the protein detergency of some non-ionic polymeric surfactants did not increase with concentration above the critical micelle concentration could have implications for optimizing the tradeoff between detergency and biocompatibility.

Hierarchical Nanoporous Silica Films for Wear Resistant Antireflection Coatings.

High-performance antireflection (AR) layers were prepared by depositing hierarchical nanoporous silica films on glass substrates. We designed a composite layer consisting of mesoporous silica nanoparticles (MSNs) and a mesoporous silica matrix. The introduction of bimodal nanoporous structures, i.e., independent nanopore formation within the MSN and within the matrix, was achieved by using surface-protected MSNs and a polymeric nonionic surfactant template during the fabrication process. A porosity of more than 40% was achieved for composite AR materials. The protrusion of MSNs from the matrix led to spontaneous formation of nanoscale roughness on the surface of the coatings, which enhanced the AR properties. The solid bonding of the MSNs to the nanoporous matrices played an important role in the achievement of high mechanical durability. The optimal nanoporous coating, which contained ca. 50 wt % MSN, exhibited high transparency (91.5-97.5%) and low reflectance (<2.2%), over the whole range of visible light wavelengths, and sufficient wear resistance.

Kinetics of formation of oil‐in‐water emulsions using in situ rheo‐optical measurements

The kinetics of mechanical emulsification in vane geometry was investigated using an original rheo‐optic device. Hexadecane‐in‐water micronic emulsions were prepared using a nonionic polymeric surfactant (Brij700®) as stabilizer. The viscosity of aqueous phase was adjusted using a commercial viscosifier (Emkarox®) which ensured Newtonian behavior to the continuous phase. The influences of two variables (rotational speed and oil volume fraction) on the kinetics of droplet fragmentation were examined in detail. Rotational speed was varied between 50 and 100 rad s−1 and had a strong effect on the kinetics of emulsion formation which was discussed on the basis of droplet fragmentation by shear forces. On the contrary, oil volume fraction (between 20 and 60% v/v) showed no marked effect, which appeared as an important result for scale‐up considerations. A theoretical description of fragmentation mechanism was proposed and experimental results were compared to calculated values. © 2014 American Institute of Chemical Engineers AIChE J, 61: 277–284, 2015

Polymeric Nonionic Surfactants as a Pour Point Depressant

Polymeric nonionic surfactants with the same hydrophobic moieties C18E68 and C18E136 were prepared. The surface properties of the synthesized surfactants and the critical micelle concentration, surface excesses concentration and the minimum surface area were evaluated and discussed. The efficiency of the prepared polymeric surfactants as pour point for fuel oil was discussed in absence and in presence of commercial additive. The most of the prepared additives showed a good performance toward improving the flow properties of the tested fuel oil. Then the rheological data were further determined through shear rate-viscosity measurements.

보조계면활성제가 Pluronic L64 비이온 계면활성제에 의한 탄화수소 오일 가용화에 미치는 영향

본 연구에서는 보조계면활성제 첨가가 n-octane, n-decane, n-dodecane 등의 탄화수소 오일의 가용화에 미치는 영향에 관하여 살펴보았다. 탄화수소의 가용화 속도는 보조계면활성제로 첨가한 알코올의 사슬 길이와 첨가량이 증가함에 따라 증가하였으며, 특히 사술 길이가 비교적 긴 알코올을 첨가하는 경우, 탄화수소 오일의 가용화 속도가 크게 증가하였다. 이는 1-butanol과 같이 짧은 사슬을 가진 수용성 알코올을 첨가할 경우에는 첨가한 대부분의 알코올이 수용액상에 존재하여 탄화수소 오일의 가용화에 큰 영향을 주지 못하는 반면에, 1-hexanol이나 1-octanol과 같이 비교적 사슬길이가 긴 알코올을 보조계면활성제로 첨가한 경우에는 첨가한 대부분의 알코올이 마이셀 상에 위치하여 마이셀을 보다 flexible한 packing을 갖게 함으로써, 가용화를 용이하게 한 것으로 생각된다. 가용화 속도 실험 결과는 spinning drop tensiometer를 사용하여 탄화수소 오일과 계면활성제 수용액 사이의 동적 계면장력을 측정한 결과와 동일한 경향을 나타내었다. 즉, 첨가한 알코올의 사슬 길이가 증가할수록 평형에서의 계면장력 값은 감소하며, 또한 계면장력 값이 평형에 도달하는 시간은 감소하였다. In this study, effect of cosurfactant on the solubilization rate of n-octane, n-decane and n-dodecane oil was performed by micellar solutions of polymeric nonionic surfactant Pluronic L64(<TEX>$EO_{13}PO_{30}EO_{13}$</TEX>) at room temperature. It has been found that the solubilization rate of a hydrocarbon oil was enhanced with an increase in both chain length and amount of alcohol added. In case of addition of a short chain alcohol such as 1-butanol, the solubilization rate of a hydrocarbon oil was slightly increased since most of alcohol molecules remained in an aqueous surfactant solution. On the other hand, the addition of a relatively long chain alcohol such as 1-hexanol and 1-octanol produced a big increase in solubilization rate of a hydrocarbon oil mainly due to incorporation of alcohol molecules into micelles and thus producing more flexible micellar packing density. Dynamic interfacial tension measurements showed the same trend found in solubilization rate measurement. Both interfacial tension value at equilibrium and time required to reach equilibrium decreased with an increase in chain length of an alcohol.