Epoxidized Sunflower Oil Research Articles

Modification of epoxidized methyl esters of sunflower oil fatty acids with some diols

It is possible to obtain products with a wide range of useful properties as a result of the modification of epoxidized vegetable oils and their derivatives. The aim of this work was to develop methods for the synthesis of new products by the reaction of epoxidized sunflower oil fatty acid methyl esters (FAME) with dihydric alcohols: ethylene glycol, butanediol-1,4, diethylene glycol, as well as in the study of their structure and properties. Dependences of the structure of the obtained products on the conditions of the process and the type of the modifier have been established. It was shown that carrying out the modification at a higher temperature (100 ° C) leads to the formation of crosslinked products as a result of intermolecular dehydration with the participation of both hydroxyl groups of the diol molecule. In addition to the opening of the oxirane ring, the transesterification process with the participation of the ester fragment is realized. Certain characteristics of the obtained products, including the acid number, saponification number, were determined, and the emulsifying effect was evaluated. In addition, the solidification temperature and pour point were determined for the products obtained. It was found that the products of modification of epoxy derivatives of FAME of sunflower oil obtained at 50 ° C have the greatest emulsifying effect.

Natural Weathering of Plasticized Polyvinyl Chloride (PVC) Stabilized with Epoxidized Sunflower Oil

The aim of this work is to study the influence of the weathering conditions on the degradation level of stabilized PVC. Epoxidized Sunflower oil (ESO) was used as a new biodegradable stabilizer for PVC. Flexible plasticized formulations (40% plasticizer) were realized, the natural weathering of the PVC samples was investigated. The samples were exposed in Tizi Ouzou (Algeria) for nine months. The samples were characterized by Fourier transform infrared spectroscopy in order to follow the structural changes. Moreover, the variation of the mass of the samples, the variation of density and mechanical properties (tensile and shore D hardness) were taken into account. Samples were characterized in terms of morphology by SEM. The best results were obtained with the formulation containing DINA and ESO compared to the traditional formulation containing DOP and ESO.

Study of the effectiveness of a presoaking process for reducing the additives migration from babies toys.

This research aims to study a process of steeping in the n-heptane, used for reducing the migration of additives contained initially in toys for babies plasticized with di-octylphtalate (DOP) based on poly (vinyl chloride) (PVC) and stabilized with epoxidized sunflower oil (ESO). Two formulations were carried out at different levels of DOP plasticizers (15% and 45%). The migration tests were conducted in the synthetic saliva in the absence and in the presence of α-amylase with or without agitation at 37° C for 1, 3, and 6 h. The migration phenomenon was studied on the basis of preliminary studies based on the mass variation of the two formulations and where the physico-chemical technical analysis: Fourier-transform infrared spectroscopy (FTIR) and gas chromatography coupled with gas chromatography-mass spectrometry (GC-MS) were performed. This work shows that the presoak method can be used successfully to reduce the migration phenomenon of the additives and to decrease the interactions between the PVC samples and the saliva stimulant. This treatment has allowed a notable decrease of the overall migration of all the additives from saliva. It is noted that the high pH value (7.17) was obtained with the F45% formulation under agitation and in the presence of α-amylase, a mass loss of the order of 0.9004 and a minimum DOP concentration of 0.024 ppm. The analysis by GC-MS provided the DOP chromatograms of the control and the specimens, which have undergone migration tests and treatments. In addition, the amount of DOP, migrated in the case of the F15% and F45%, controls the formulations and was greater than those of the presoaked formulations, which have indicated the efficiency of the applied process. This study shows that migration has taken place, and that the soaking treatment has reduced the migration of all the additives present in the PVC samples.

SYNTHESIS AND CHARACTERIZATION OF BIOBASED EPOXIDIZED EDIBLE OILS

Nowadays, major pollutions present in the environment are produced by non-degradable substances. Eventually, the use of non-degradable products will increase carbon footprint in the atmosphere. In this study, modifications of five vegetable oils into biobased epoxides are reported. The oils used in this study were commercial palm oil, rice bran oil, canola oil, soybean oil and sunflower oil. The vegetable oils were refluxed using formic acid and hydrogen peroxide at temperature ranges of 45 to 50˚C and 60 to 65˚C for seven hours in order to change the chemical structure of carbon-carbon double bonds into oxirane rings. The mixture was then processed by liquid-liquid extraction to separate epoxide oil from liquid that was present during the reflux process. The obtained oils were then analyzed using ATR-FTIR and the presence of oxirane rings were observed at the wavelength ν=1080.79 cm-1 and 836.10 cm-1 for epoxidized palm oil, ν =1107.14 cm-1 and 841.11 cm-1 for epoxidized rice bran oil, ν =1050.13 cm-1 and 850.35 cm-1 for epoxidized canola oil, ν =1083.99 cm-1 and 825.03 cm-1 for epoxidized soybean oil and ν =1095.57 cm-1 and 820.16 cm-1 for epoxidized sunflower oil, respectively. Additionally, an absorption band at ν=1462 cm-1 was observed in all oil samples, indicating the presence of C-C oxirane. In future, these epoxidized oils can serve as a great potential as new starting materials for the synthesis of lipid biopolymers.

Investigation of Artificial Ageing of PVC Stabilized with Epoxidized Sunflower Oil as Biobased Derivative

Objective: The objective of this work is to study the artificial ageing of semi-rigid and plasticized polyvinyl chloride (PVC) stabilized with epoxidized sunflower oil (ESO) as a biobased derivative in combination with zinc and calcium stearates. Methods: For comparison, a formulation of PVC plasticized and stabilized with epoxidized soya bean oil (ESBO) was considered. Artificial ageing was carried out during the 304 hours. Samples were taken off after: 48, 146, 234 and 304 hours and then characterized. The evolution of density, glass transition temperature and morphology, was followed as a function of the time. The structural modifications of polymer were analyzed by Fourier transform infrared spectroscopy in attenuated total reflectance and transmission modes. Results: The results showed a little decrease of density, a considerable increase of the glass transition temperatures values and a change of morphology. All changes in the properties of PVC relate to formation of new chemical structures. Conclusion: Globally, it was found that ESO exhibited similar performances to those of ESBO.

Properties Investigation of Epoxidized Sunflower Oil as Bioplasticizer for Poly (Lactic Acid)

This study aims to improve low intrinsic ductility of poly (lactic acid) (PLA) by using a novel bio-sourced plasticizer environmentally friendly and cost-effective and to get a fully biodegradable material with potential application in films manufacturing. For that purpose, commercial sunflower oil (SO) was epoxidized and epoxidized sunflower oil (ESO) was used as plasticizer for PLA. To investigate ESO potential as plasticizer for PLA, its plasticizing effect was compared with commercial epoxidized soya bean oil (ESBO). Bioblends based on PLA and epoxidized vegetable oils (EVO) as bioplasticizers were prepared. The plasticizers (ESO or ESBO) were respectively compounded with PLA at 10, 20, 30, and 40 wt%. Mechanical (tensile and Shore D hardness), thermal (differential scanning calorimetry (DSC), thermogravimetric analysis (TGA)) and morphological properties (optical microscopy and scanning electron microscopy (SEM)) were characterized. The results showed that the addition of ESO or ESBO to PLA decreased tensile strength and tensile modulus compared to neat PLA but increased elongation at break for which an optimum (9 %, 16 and 34 % for ESBO, ESO5.5 % and ESO6.5 % respectively) was reached at a content of 20 wt% of plasticizer. The structures of the obtained plasticized PLA were confirmed by FTIR spectroscopy. The thermal properties (DSC), such as glass transition temperature (Tg) and melting temperature (Tm) were slightly decreased by addition of plasticizer into PLA, indicating that plasticizer increases the chain mobility and SEM analysis proved successful modification on the PLA brittle morphology with addition of EVO. On the other hand, TGA results revealed increase in the thermal stability. Also the results showed the effect of the EVO weight and the epoxy content (O.O value) on the improvement of the properties of PLA. ESO6.5 % at 20wt% was an efficient plasticizer for PLA.

Enhancement of Cu Nanoparticles Dispersion in Nanolubricants by Magnetron Sputtering Deposition and Its Influence on the Tribological Behavior

Abstract We investigated the chemical, physical, and tribological properties of nanolubricants consisting of epoxidized sunflower oil with Cu nanoparticles as additive. These latter are produced by magnetron sputtering at distinct current levels in the deposition, to improve the development of nanolubricants by enhancing the nanoparticles dispersion. The nanolubricants are here characterized by Fourier transform infrared spectroscopy, zeta potential, ultraviolet–visible absorbance spectroscopy, small-angle X-ray scattering, and scanning electron microscopy. After all, the tribological properties of the bionanolubricants are investigated using a high-frequency reciprocating rig equipment, scanning electron microscopy, and energy dispersive spectroscopy. Our results disclose the nanolubricants produced using the magnetron sputtering technique have excellent nanoparticle dispersion, as well as good tribological performance.

Assessment of derived sunflower oil as environmentally friendly plasticizers in Poly Vinyl Chloride

Epoxidized sunflower oil (ESO) and epoxidized sunflower oil methyl ester (ESOME) were synthetized and employed as secondary bio based plasticizers and combined with primary natural plasticizers. As such, di-esters isosorbide (DEI) and acetyl tributyl citrate (ATBC) used in Poly Vinyl Chloride (PVC) as compared to di-(2-ethylhexyl) phthalate (DEHP). PVC Sheets were obtained by processed the polymer and its additives on two-roll mill. The effect of the plasticizers combination on flexible sheets properties, including stabilization, migration, fusion rheological properties and light transmission have been discussed, Results have shown that ESO and ESOME have improved PVC formulations thermal stability, the weight loss by volatility has decreased in the formulations which contained ESO or ESOME. Mixtures of plasticizers have lower migration rates. Plastograph test has indicated a better compatibility of PVC with these plasticizer mixtures. The light transmission rate through PVC sheets plasticized by bio-based plasticizers mixtures is more than those containing DEHP.

Impact study of new formulations based on plasticized polyvinyl chloride (PVC)

The aim of this paper is the determination of the migration and biodegradation of the PVC additives in the soil. Epoxidized Sunflower Oil (ESO) was used as a thermal organic co-stabilizer for PVC; it was obtained by epoxidation of commercial sunflower oil. Two plasticizers were used: dioctyl phthalate (DOP) and diisononyl adipate (DINA). A natural aging test on site in a garden soil (Tizi Ouzou, Algeria) of the PVC samples was investigated for 6 months. The samples were characterized by Fourier transform infrared (FTIR).The morphological changes were followed by scanning electron microscopy (SEM). The evolution of the bacterial growth, identification using biochemical tests, variation of pH and variation of mass were investigated. The results showed that the nature of the plasticizer and heat stabilizer affects the properties of PVC as well as the phenomena of migration and biodegradation.

Optimisation of Operatory Conditions for Synthesis of Sunflower Oil Biobased Polyols Using Design of Experiments and Spectroscopic Methods

The present work studies the synthesis of biopolyols based on epoxidized sunflower oil (ESFO) and obtained via alcoholysis reaction. The ring opening reaction ESFO (with an oxirane index: O.O% of 6.2%) was carried using an alcohol solution and boron trifluoride (as catalyst). The operatory conditions of synthesis were optimized using a design of experiment (DOE). Alcohol content, catalyst percent as well as temperature were varied according to a JMP software matrix. Reaction conversion was followed by determination of the decrease of epoxy ring using titration method as well as an increase of the hydroxide group. The synthesized polyols were characterized using Fourier transform infrared spectroscopy and proton nuclear magnetic resonance. The results showed that oxirane ring has totally disappeared (in some formulations) which means full conversion. The full factorial design is an efficient method for testing the effect of operatory conditions especially in limiting the number of synthesis experiments.

Fabrication of oil‐ and water‐resistant paper without creating microplastics on disposal

AbstractThe proliferation of microplastics in the ocean and other water bodies is becoming an alarming issue. The development of plastic‐free water‐ and oil‐resistant paper can contribute toward mitigating this problem. Herein we report a plastic‐free paper coating derived from chitosan and sunflower oil. Chitosan grafted sunflower oil paper coatings were prepared via the ring opening of the partially epoxidized sunflower oil with chitosan. The product of these reactions was characterized by nuclear magnetic resonance and infrared spectroscopy techniques. The sunflower oil grafted chitosan solution was coated onto a Kraft paper. The Cobb 60 and kit rating values were determined to be 8.00 g/m2 and 7.66, respectively, for the optimal formulations. Meanwhile, the water contact angle was found to be 94.0 ± 1.6° after 30 s. Scanning electron microscopy analysis was employed to gain insight regarding the changes that occurred on the paper surface at the microscopic level.

Elaboration and Characterization of Polyurethane Foams Based on Renewably Sourced Polyols

The aim of this work is to prepare and characterize a series of bio-polyurethane foams (Bio-PUFs) based on renewably sourced polyols in order to increase their ecological potential, while maintaining their properties. Polyurethane foams (PUFs) were obtained using two sunflower based-polyols (SF-P1 and SF-P2) with different hydroxyl numbers synthesized through the acid-catalyzed ring-opening of epoxidized sunflower oil (ESFO) and subsequent partial reduction of the ethylenic linkages to give hydroxyl moieties. These SF-Ps were applied for replacement of petrochemical polyol Confort P0010 with a mass fraction of SF-P in the range of 40–100%. The resins were characterized by Fourier transform infrared (FTIR) spectroscopy. Their solution viscosity and thermal behavior were investigated. The obtained SF-Ps were reacted with diisocianates to yield PUFs at a fixed NCO index. Several experiments were conducted by varying the amounts of polyols, isocyanate, catalysts, and surfactants until acceptable foams were obtained. The structures of the obtained PUFs were confirmed by FTIR spectroscopy and scanning electron microscopy (SEM). The morphology, the apparent density, the thermal behavior (thermogravimetric analysis and differential scanning calorimetry), and the thermal conductivity of the PUFs were investigated. The study showed that it is possible to substitute petrochemical polyols by the addition of SF-P to achieve PUFs with desirable properties. It was found that the mixing of SF-Ps in formulations influences especially the thermal and morphological properties, and increases the end product renewable material content. The highest renewable material content showed SF-PUFs (reaching 76%) since the renewable material content in SF-P is high (~ 92%). As a result of the SF-Ps loading in the range of 40–100% the PUFs change from flexible to semi-flexible structures. Furthermore, they become denser and exhibit numerous cell shapes, such as semi-open cells and closed cells.

Spectroscopic and mechanical properties of PVC plasticized by bio-plasticizer ESO

In this work, we describe the synthesis of epoxidized sunflower oil (ESO) and its incorporation as a bio-plasticizer of PVC by the partial substitution of bis (2-ethylhexyl) phthalate (DEHP). The formulations are based on PVC and a plasticizer binary system (ESO/DEHP) varying from (00/60) Phr to (30/30) Phr. The epoxidation of the sunflower oil gives an oxyrane oxygen (O.O) in order of 6.2%. The optical properties of the so-obtained PVC formulations (ESO) are experimentally characterized by infrared Fourier transformer (FTIR) and Ultraviolet Visible (UV-Visible). The mechanical properties are determined using the tensile strength, Hardness shore D and A. The results show that after a partial substitution of DEHP by ESO (up to 20 Phr), the films maintaining the suppleness of the PVC and without reaching a stage of thermal degradation.

Preparation of epoxidized sunflower oil metal soap derivatives and their use asheat stabilizers for polyvinyl chloride

The aim of this work was to prepare metal soaps of epoxidized sunflower oil (ESO) and use them as thermal stabilizers for polyvinyl chloride (PVC). For that purpose, commercial sunflower oil was first epoxidized and then used to prepare (Ba, Zn, Pb, and Cd) metal soap derivatives, which were characterized by Fourier transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC). The prepared metal soaps derivatives of ESO were used as thermal stabilizers for plasticized PVC. Discoloration, residual thermal stability at 200 $^{\circ}$C , and rheological properties of PVC samples were tested. The structural modifications were investigated by UV-visible spectroscopy. The best thermal stabilization effects were observed in the presence of Pb soap of ESO. Furthermore, metal derivatives of ESO were classified according to their stabilizing effect as follows: Pb-ESO > Ba-ESO > Cd-ESO > ESO > Zn-ESO.

Characterization of Polymer Composite Materials Based on Epoxy Resin GELR 128 Modified with Epoxidized Sunflower Oil Cured by 4.4’-Diaminodiphenylmethane

Characterization of Polymer Composite Materials Based on Epoxy Resin GELR 128 Modified with Epoxidized Sunflower Oil Cured by 4.4’-Diaminodiphenylmethane

Synthesis of fully bio-based and solvent free non-isocyanate poly (ester amide/urethane) networks with improved thermal stability on the basis of vegetable oils

The purpose of this study is to synthesize non-isocyanate poly (ester amide/urethane) networks, based entirely on vegetable oil through a green method, i.e., without solvent and having any rigid and aromatic structures to improve their thermal stability. For this purpose, first, three amines were synthesized from castor oil and oleic acid. Second, carbonated sunflower oil (CSFO) was obtained by reaction of epoxidized sunflower oil with CO2 at atmospheric pressure. In the final step, CSFO easily reacted with bio-based amines by melt-blending without catalyst to give corresponding non-isocyanate polyurethane (NIPU) networks. The Fourier-transform infrared spectroscopy (FTIR), nuclear magnetic resonance (NMR), X-ray powder diffraction (XRD), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA) and thermogravimetric analysis (TGA) techniques were applied to characterize the structural, thermal and physical features of NIPU networks. In addition, to determine the environmental stability the water absorption amount and the degradation percentage were calculated in the deionized water and phosphate saline buffer, respectively. These NIPU networks showed an excellent thermal stability (T5 wt% between 323 and 386 °C), low water absorption and degradation (4–10 and 1.04–1.40 wt% respectively). The results show the potential of this environmentally friendly strategy for preparing bio-based NIPU for high performances. Furthermore, the presence of an aliphatic ester group and their biodegradability nature may also make them proper for biological and/or biomedical applications.

Development of sunflower oil‐based nonisocyanate polyurethane/multiwalled carbon nanotube composites with improved physico‐chemical and microwave absorption properties

In this article, we have developed sunflower oil based non‐isocyanate polyurethane (NIPU)/amine functionalized multiwalled carbon nanotube (AF‐CNT) composites. First, carbonated sunflower oil (CSFO) was obtained by solvent‐free mixture reaction of CO2 with epoxidized sunflower oil under the conditions (120°C, 40 bar) for 10 h, and characterized by FTIR, 1H NMR and 13C NMR. Then, NIPUs were synthesized by reacting the CSFO with isophorone diamine (IPDA) and subsequently, the effects of different weight percentages (0–2 wt%) of AF‐CNTs on physico‐chemical properties of the NIPU/AF‐CNT composites were examined. FT‐IR, XRD and SEM analyses confirmed the formation of the polymer nanocomposites. The results of the studies showed that polymer nanocomposites exhibited better performance than that of pristine polymer. In addition to the improvement in physico‐chemical properties, the electromagnetic interference shielding properties of the composites (1.5 wt% AF‐CNTs) were also calculated in the 8.2–12.4 GHz (X‐band) frequency range with different thicknesses. It is seen that the composite (1.5 wt%) with thickness 3 mm shows the highest microwave absorption with −17 dB at 10.86 GHz. POLYM. COMPOS., 40:E1120–E1130, 2019. © 2018 Society of Plastics Engineers

Solvent and catalyst-free synthesis of sunflower oil based polyurethane through non-isocyanate route and its coatings properties

Bio-based Non-Isocyanate Polyurethanes (NIPUs) were synthesized by bulk polyaddition of diamine with carbonated sunflower oil (CSFO). Carbonated vegetable oils were obtained by solvent-free mixture reaction of CO2 with epoxidized sunflower oil under the conditions (120 °C, 50 bar) and characterized by FTIR, 1H NMR, and 13C NMR. Finally, the effect of the amine structure as well as CSFO/amine molar ratio (1:0.75, 1:1 and 1:2) on mechanical, and chemical properties NIPU’s were studied by using curing agents EDA (1,2-ethylenediamine), DETA (Diethyltriamine) and IPDA (Isophorone diamine). Except for IPDA based NIPU, it was seen that along with urethane formation, the amine group also reacted with ester groups to form amides. IPDA and EDA showed good thermal, mechanical, chemical and anticorrosive properties. Furthermore, DETA based NIPU displayed high elongation at break. These results highlight the potentiality of this environmentally friendly approach to prepare renewable NIPU materials for surface coatings purpose.

Novel Biocomposites Based on Sunflower Oil and Alfa Fibers as Renewable Resources

The aim of this work is to develop biocomposites based on modified sunflower oil as resin and short natural fibers from Alfa plants (Stipa tenacissima) as reinforcement. Epoxidized sunflower oil (ESFO) was chemically modified via acrylation reaction to obtain acrylated epoxidized sunflower oil resin (AESFO). The AESFO resin was then copolymerized with styrene as co-monomer in the presence of boron trifluoride (BF3) as cationic initiator and cobalt octoate (Co) as catalyst. Experimental conditions of this modification were optimized by varying styrene, Co and BF3 wt%. The styrene was varied from 30, 40 to 50 wt% while the catalyst (Co) was varied from 0, 0.01, 0.02 to 0.03 wt%. Two different percents of BF3 were considered: 0.5 and 1 wt%. The prepared samples were evaluated according to their appearance and then characterized in terms of tensile properties (stress at break, Young’s modulus and elongation at break) to determine the best ratio of styrene/BF3/Co. Alfa fibers, used as bio-reinforcement, were treated with a 5% NaOH solution and characterized by Fourier transform infrared (FTIR) spectroscopy, scanning electron microscopy (SEM) and thermo gravimetric analysis (TGA). Biocomposites were prepared by using untreated (UAF) and treated Alfa fibers (TAF) at a ratio of 5 wt% and characterized in terms of tensile properties and morphology by SEM. The best results were obtained with TAF. Then, the ratio of TAF was varied (5, 7.5 and 10 wt%) and the tensile and thermal properties of the biocomposites were characterized. The results showed that the best results were obtained with the ratio of 7.5 wt%.

Thermal and mechanical properties of bio-based plasticizers mixtures on poly (vinyl chloride)

The use of mixtures of nontoxic and biodegradable plasticizers coming from natural resources is a good way to replace conventional phthalates plasticizers. In this study, two secondary plasticizers of epoxidized sunflower oil (ESO) and epoxidized sunflower oil methyl ester (ESOME) were synthesized and have been used with two commercially available biobased plasticizers; isosorbide diesters (ISB) and acetyl tributyl citrate (ATBC) in order to produce flexible PVC. Different mixtures of these plasticizers have been introduced in PVC formulations. Thermal, mechanical and morphological properties have been studied by using discoloration, thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical thermal analysis (DMTA), tensile - strain and scanning electron microscopy (SEM). Studies have shown that PVC plasticization and stabilization were improved by addition of plasticizers blends containing ISB, ATBC, ESO and ESOME. An increase in the content of ESO or ESOME improved thermal and mechanical properties, whereas ESOME/ATBC formulations exhibited the best properties.