Styrenated sunflower oil polymers from raft process for coating application

Oil-based macroinitiator (MI) obtained from sunflower oil was styrenated using reversible addition–fragmentation chain transfer polymerization (RAFT) in the presence of phenacyl morpholine dithiocarbamate (PMDC) as chain transfer agent. The solvent effect and effect of the molar ratio of the transfer agent, PMDC, on polydispersity and molecular weight of the polymers were investigated. The obtained results showed that, 1,4-dioxane is a better solvent and 1/4 molar ratio of [MI]/[PMDC] provides relatively low polydispersities. No homopolystyrene was detected under these conditions, indicating the efficiency of PMDC in the chain transfer process. Livingness of the polymerization process was confirmed by chain extension with styrene using the preformed polymer as macrotransfer agent. The film properties of styrenated oil samples were determined according to the related standards. To improve film properties, the polymer obtained by RAFT technique was modified by reaction with MI. The resulting material gave transparent films with good film properties. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2012     

Phenolic epoxidised polyurethane coating for petroleum tanks from available raw materials

Summary  Linseed oil was epoxidised by 60% per acetic acid to produce epoxidised linseed oil. By this process, two new groups entered the molecule (epoxy group and hydroxyl group). These groups were detected by using infrared (IR) analysis. Product (I) reacted with phenol in different ratios by weight percent to produce Phenolic epoxidised resin (II). Product (II) reacted with toluene diisocyanate to produce product (III), Phenolic epoxidised polyurethane, which had an excellent adhesion character. Product (III) was examined chemically and physically according to ASTM-API standard methods. The results provide encouragement for their use as a petroleum tank coating material. They can be used as a one-layer coating which combines the properties of more than coating of two layers because it combines more than one function group.     

Modification of polycaprolactone-styrene-vinyl trimethoxysilane terpolymer with sunflower oil for coating purposes

Polycaprolactone-styrene-vinyl trimethoxysilane terpolymer was prepared and then modified with sunflower oil partial glyceride (SFOPG) via a sol–gel method for use as a binder in coating applications. Therefore, a vinyl-functionalized polyester-based macromonomer (HPCL) was prepared via ring-opening polymerization of ?-caprolactone (CL) using 2-hydroxyethyl methacrylate (HEMA) followed by copolymerization with styrene (St) and vinyl trimethoxysilane (VTMS) to yield a terpolymer (HPCL-St-VTMS). The terpolymer was characterized by FTIR, GPC and ¹H NMR. To overcome the fact that the cured film of HPCL-St-VTMS was slightly soft, SFOPG was used as a modifier and was inserted to the structure via a sol–gel reaction between the hydroxyl groups and methoxy silane moieties of the terpolymer. After this modification, the softness disappeared. Nanosize inorganic domains were observed in the SEM image. Thermal analyses of the resulting cross-linked film of SFOM-HPCL-St-VTMS were performed with DSC and TGA. SFOM-HPCL-St-VTMS, which does not melt, resulted in a higher char yield and decomposition temperature at 5% weight loss compared to the unmodified HPCL-St-VTMS film. An evaluation of the film properties indicated that SFOM-HPCL-St-VTMS can be used as a coating material.     

Pre-Pressing of oil from rapeseed and sunflower

The current methods of prepressing rapeseed and sunflower seed prior to solvent extraction are reviewed on a stage-by-stage basis. The energy consumption numbers are examined and the overall extractability of the presscake is discussed. Possible changes in processing methods, with advantages and drawbacks, are set out.     

Recovery of phytosterols from sunflower oil deodorizer distillates

Phytosterols are usually recovered by crystallization from the deodorizer distillate (DD) of vegetable oils. In this work, the impact of the principal process variables (viz., solvents and cosolvents, cooling rate, crystallization temperature, and ripening time) on the quality and yield of the recovered phytosterols was studied by using a sunflower oil DD “enriched” (i.e., preconcentrated) via transesterification with ethanol (EDD) as a feedstock and commercial hexane as solvent (S), with S/EDD mass ratios of 3 to 5. Water (0 to 4.5 wt%) and ethanol (0 to 10 wt%) were used as cosovents, with crystallization temperatures between 0 and −20°C and crystallization times from 4 to 96 h. The cooling rate was either −20°C/h or “brisk chilling” from 40 to −5°C. The nature and composition of the EDD solvent and cosolvent composite arose as the most important process variable, strongly influencing both the percentage of sterol yield and the purity of the crystals, as well as their filterability and washability. Water-saturated hexane sufficed to give good crystallization, yet the beneficial effect of adding water as the single cosolvent was enhanced by adding small and precise amounts of ethanol. A recovery of sterols as high as 84% (with 36% purity) was achieved by using a single-stage batch crystallization of the S/EDD mixture (S/EDD=mass ratio 4).     

Stereospecific analysis of TAG from sunflower seed oil

Stereospecific analysis of TAG from a sunflower seed oil of Tunisian origin was performed. The TAG were first fractionated according to chain length and degree of unsaturation by RP-HPLC. The four major diacid- and triacid-TAG fractions were palmitoyldilinoleoyl-glycerol, dioleoyllinoleoylglycerol, oleoyldilinoleoylglycerol, and palmitoyloleoyl-linoleoyl-glycerol, amounting to 7.2, 16.6, 29.5, and 12 mol%, respectively. The TAG of the four fractions were individually submitted to stereospecific analysis, using a Grignard-based partial deacylation, separation of sn-1,2(2,3)-DAG from sn-1,3-DAG by boric acid-impregnated silica gel TLC plates, conversion of the sn-1,2(2,3)-DAG to their 3,5-dinitrophenylurethane (DNPU) derivatives, fractionation of DNPU derivatives by RP-HPLC, resolution of the DNPU-DAG by HPLC on a chiral column, transmethylation of each sn-DNPU-DAG fraction, and analysis of the resulting FAME by GC. The data obtained were used to determine the triacyl-sn-glycerol composition of the main TAG of the oil. Fifteen triacyl-sn-glycerols were identified and quantified, representing, along with the monoacid-TAG, trilinoleoylglycerol and trioleoylglycerol, more than 90% of the total oil TAG. The two major triacyl-sn-glycerols were trilinoleoyl-glycerol and 1-linoleoyl-2-linoleoyl-3-oleoyl-glycerol (18.6 and 18.5% of the total, respectively). Results clearly identified linoleic acid as the major FA at the sn-2 position, whereas oleic and palmitic acids were the major FA at the sn-3 position. The sn-1 position was occupied to nearly the same extent by linoleic and oleic acids, and to a greater extent by palmitic acid, which was practically absent at the sn-2 position.     

Winterization of sunflower oil

The chemical composition and percentage of waxes in sunflower oil are presented in relation to the crude oil quality obtained from decorticated or undecorticated sunflower seed. Three methods of winterizing are described: the conventional method with separation by filters, crystallization with a wetting agent and separation by centrifuge and winterization in solvent. We also comment on methods for checking the quality of winterized sunflower oil.     

Effect of oil replenishment during deep-fat frying of frozen foods in sunflower oil and high-oleic acid sunflower oil

Frying stability of sunflower oil (SO) with 23% oleic acid and 61% linoleic acid, and of high-oleic acid sunflower oil (HOSO) with 74% oleic acid and 13% linoleic acid was studied during 20 discontinuous deep-fat fryings of various frozen foods, with or without frequent replenishment of the used oil with fresh oil. Alterations of both oils were measured by column, gas-liquid and high-performance size-exclusion chromatography. Total polar content and compounds, related to thermoxidative changes, and diacylglycerides, related to hydrolytic changes, increased in all oils during frying but reached higher levels in SO than in HOSO. Nevertheless, the increased levels of diacylglycerides observed may result from the frozen potatoes prefried in palm oil. Oleic acid in HOSO and linoleic acid in SO significantly decreased, but the fatty acid modifications that occurred during the repeated fryings were not only related to thermoxidative alteration but also to interactions between the bath oil and the fat in the fried products. Data from this study also indicated that HOSO performed more satisfactorily than SO in repeated fryings of frozen foods. Moreover, frequent addition of fresh oil throughout the deep-frying process minimized thermoxidative and hydrolytic changes in the frying oils and extended the frying life of the oils.     

Interesterification of tallow and sunflower oil

The objective of this study was to manufacture a shortening using chemical interesterification (IT) of tallow-sunflower oil blends to replace fish oil in the present formulation, which is now in short supply in Chile. The significant variables of the IT process were obtained by 2⁴⁻¹ fractional factorial design. The proportion of tallow (T) in the blend, catalyst concentration, and reaction temperature had a significant effect on the melting point (mp) (P≤0.05). IT of tallow and sunflower oil blends (90∶10 and 70∶30) diminished the mp, dropping point, and refractive index compared to tallow. However, a noninteresterified 90∶10 blend mp was not significantly different from tallow. IT produced a solid fat content (SFC) profile of IT90∶10 blend that was appropriate for use in shortenings for the baking industry. Blending and IT of the 90∶10 blend increased the melting profile of the tallow and the melting range from −40 to 60°C while the endotherms of the middle-melting triacylglycerols (TAG) decreased. The IT90∶10 blend hardnesswas 70% lower than tallow hardness, and the crystal network was composed of large spherulites in a network. IT resulted in an appropriate method to improve physical properties of tallow, whereas blending did not significantly modify it. The interesterification changed the SFC profile of IT90∶10, giving a more appropriate shortening for use in the baking industry.     

Supercritical fluid extraction and characterisation of oil from hazelnut

Hazelnut (Corylus avellana L.) oil was extracted with compressed carbon dioxide in the temperature range of 308—321 K and in the pressure range of 18—23.4 MPa. In addition the influence of the superficial velocity, within a tubular extractor was studied. Physical and chemical characteristics of the oil were obtained. The results including contents of free fatty acids, sterols, triacylglycerols and tocopherols were compared with those obtained when n‐hexane was used as solvent. No significant differences were found when the oils extracted by both methods were analysed. The main fatty acid was the oleic acid (83—85%), followed by linoleic acid (6—8%) and palmitic acid (5—6%). The main triglyceride found in hazelnut oils was the trioleylglycerol (OOO) (63.4—69.6%), followed by the linoleyl‐dioleylglycerol (LOO) (11.6—15.5%) and palmitoyl‐dioleylglycerol (POO) (9.9—10.4%). In terms of sterols, the main component was β‐sitos‐terol (∼83%) followed by campesterol (∼6%). The amount of cholesterol was very low (∼0.2%). The CO₂ extracted oil contained about 17% more tocopherols (458.7 μg/g oil) than the oil extracted by n‐hexane (382.8 μg/g). Oxidative stability was studied by using the induction time determined by the Rancimat method. The oil obtained by supercritical fluid extraction (SFE) was slightly more protected against oxidation (8.7 h for SFE extracted oil and 6.7 h for the hazelnut oil extracted with n‐hexane). Both oils presented high stability index values (7.81 for the oil extracted by n‐hexane and 8.7 for the oil extracted with supercritical CO₂). Oil extracted by supercritical CO₂ was clearer than the one extracted by n‐hexane, showing some refining. Besides, the acidity index was 1.6 for the n‐hexane extracted oil and 0.9 for the oil extracted with supercritical carbon dioxide. The central composite non‐factorial design was used to optimise the extraction conditions, using the Statistica, version 5 software (Statsoft). The best results, in terms of recoveries of hazelnut oil by SFE, were found at 22.5 MPa, 308 K and superficial velocity of 6.0 × 10^—4 ms^—1.     

Extrusion and property characterisation of waste-based ceramic formulations

This work describes the studies carried out with various industrial wastes and natural sub-products based on the SiO₂–Al₂O₃–CaO system, aimed at extruding all-waste ceramic products of industrial interest. Four waste materials were selected and characterised, namely, (i) Al-rich anodising sludge (A-sludge), (ii) sludge from the filtration/clarification of potable water (W-sludge), (iii) sludge generated in marble sawing processes (M-sludge), and (iv) foundry sand (F-sand).The plastic behaviour of two different all-waste formulations was first characterised by stress–strain curves and then, after prior adjustment of the plasticity level, the effect of the ram speed and extrusion pressure was evaluated using the Benbow–Bridgwater's model for paste extrusion. Using the waste-based formulations with additives and tube-dies of different die-land dimensions, a good agreement was demonstrated between predicted and measured values. The differences in the static friction coefficient give an effective indication of the surface quality of the extrudate.Extruded rods were then fired at several temperatures and characterised in terms of relevant functional properties (shrinkage, density and mechanical strength). Compositional evolution was assessed by X-ray diffraction. Since interesting performances were observed, the potential of the use of wastes in ceramic formulations of industrial interest was confirmed.     

Crystallization of sunflower oil waxes

Activation free energies of nucleation (ΔG _c ) were calculated using induction times of crystallization measurements. Results showed that ΔG _c decreased exponentially as wax concentration increased at a constant crystallization temperature (T _c ). In contrast, for a constant supersaturation, ΔG _c increased from 12 to 22°C but decreased between 22 and 35°C. Melting behavior of purified waxes and solutions of purified waxes in sunflower oil were studied by DSC after crystallization at fast and slow cooling rates (20 and 1°C/min, respectively). Low supercooling temperatures (T _c >65°C) showed an increase in the onset temperature (T ₀ ) as T _c increased for both fast and slow cooling rates. Broader peaks were obtained for samples crystallized at a slow cooling rate at the same T _c . Regarding the solutions of waxes in sunflower oil, the wax concentration (supersaturation of the system) controlled crystallization as well as T _c . As T _c increased, the enthalpy (ΔH) decreased at a constant wax concentration. When wax concentration decreased, ΔH decreased at a constant T _c . For a low driving force, a small shoulder was obtained in the DSC diagrams owing to some type of fractionation. These results showed that wax crystallization is affected by different experimental parameters, such as T _c and cooling rate, depending on the wax concentration of the sample.     

Isolation of tocopherol and sterol concentrate from sunflower oil deodorizer distillate

The isolation of tocopherols and sterols together as a concentrate from sunflower oil deodorizer distillate was investigated. The sunflower oil deodorizer distillate was composed of 24.9% unsaponifiable matter with 4.8% tocopherols and 9.7% sterols, 28.8% free fatty acid (FFA) and 46.3% neutral glycerides. The isolation technology included process steps such as biohydrolysis, bioesterification and fractional distillation. The neutral glycerides of the deodorizer distillates were hydrolyzed byCandida cylindracea lipase. The total fatty acids (initial FFA plus FFA from neutral glycerides) were converted into butyl esters withMucor miehei lipase. The esterified product was then fractionally distilled in a Claisen-vigreux flask. The first fraction, which was collected at 180–230°C at 1.00 mm of Hg for 45 min, contained mainly butyl esters, hydrocarbons, oxidized products and some amount of free fatty acids. The fraction collected at 230–260°C at 1.00 mm Hg for 15 min was rich in tocopherols (about 30%) and sterols (about 36%). The overall recovery of tocopherols and sterols after hydrolysis, esterification and distillation were around 70% and 42%, respectively, of the original content in sunflower oil deodorizer distillate.     

Biodiesel from sunflower oil by using activated calcium oxide

This work studies the activity of activated CaO as a catalyst in the production of biodiesel by transesterification of triglycerides with methanol. Three basic aspects were investigated: the role of H₂O and CO₂ in the deterioration of the catalytic performance by contact with room air, the stability of the catalyst by reutilization in successive runs and the heterogeneous character of the catalytic reaction. The characterization by X-ray diffraction (XRD), evolved gas analysis by mass spectrometry (EGA-MS) during heating the sample under programmed temperature, X-ray photoelectron (XPS) and Fourier transform-infrared (FT-IR) spectroscopies allowed to concluding that CaO is rapidly hydrated and carbonated by contact with room air. Few minutes are enough to chemisorb significant amount of H₂O and CO₂. It is demonstrated that the CO₂ is the main deactivating agent whereas the negative effect water is less important. As a matter of fact the surface of the activated catalyst is better described as an inner core of CaO particles covered by very few layers of Ca(OH)₂. The activation by outgassing at temperatures ≥973 K are required to revert the CO₂ poisoning. The catalyst can be reused for several runs without significant deactivation. The catalytic reaction is the result of the heterogeneous and homogeneous contributions. Part of the reaction takes place on basic sites at the surface of the catalyst, the rest is due to the dissolution of the activated CaO in methanol that creates homogeneous leached active species.     

Metathesis of fatty esters derived from South African sunflower oil

The metathesis of the mixture of fatty monoesters derived from sunflower oil was examined using the WCL₆-(CH₃)₄Sn catalytic system. After distillation of the reactant mixture, a total conversion of 81% and a 17% yield of diesters was achieved using a 1∶1∶30 mole ratio of catalyst:cocatalyst:ester. The rate of reaction of the ethyl linoleate was double that of the oleate.     

Experimental and modelling of supercritical oil extraction from rapeseeds and sunflower seeds

The supercritical oil extraction from oleaginous seeds (sunflower and rapeseeds) is presented here through experimental and modelling results. The experimental setup allows an accurate following of the mass of the oil extracted and to derive the experimental influences of pressure, temperature and supercritical CO₂ flowrate on the extraction curves. These parameters are very sensitive and highlight the necessity of precise optimisation of experimental conditions. In order to complete the behaviour of supercritical fluids extraction, an improved modelling is proposed. The modelling basic equations are based on others modelling published previously. In this work, the determination of several parameters comes from correlations and the other constants are fitted with all the experimental results. Thus the modelling is more representative and predictive as other ones. The modelling results present a good agreement with the experimental results, and hence it can be used for the dimensioning of some extraction autoclaves.     

Removal of waxes from sunflower seed oil by miscella refining and winterization

Miscella refining and winterization produced a sunflower seed salad oil that did not cloud on refrigeration for 7 days. Refining reduced phospholipid content, and this facilitated wax removal during winterization.